Multi-substituted tetrahydrofurans and tetrahydropyrans

ABSTRACT

Novel odorant compositions which are characterized by a content of one or more compounds selected from the group consisting of tetrahydrofurans of structures 1 or 2, or tetrahydropyrans of structure 3. ##STR1## wherein R can be an acyclic, where acyclic refers to a chain of at least four carbon atoms substituted with at least three methyl groups in the chain, carbocyclic, where carbocyclic refers to a ring of 5-8 carbon atoms, and with at least two methyl groups on the ring, or bicyclic where bicyclic refers to two carbon tings, each ring having between 5-8 carbon atoms fused together, substituted with at least two methyl groups, and where R 1  =CH 3 , or higher alkyl group, R 2  =H, CH 3 , or higher alkyl group, R 3  =H, or CH 3 , R 4  and R 5  =H, CH 3 , or higher alkyl group.

This is a divisional of U.S. application Ser. No. 08/363,685, filed Dec.23, 1994 now U.S. Pat. No. 5,510,326.

FIELD OF THE INVENTION

The present invention is concerned with novel tetrahydrofurans (THF) ofstructures 1 or 2, or tetrahydropyrans (THP) of structure 3. ##STR2##wherein R can be an acyclic, where acyclic refers to a chain of at leastfour carbon atoms substituted with at least three methyl groups in thechain, carbocyclic, where carbocyclic refers to a ring of 5-8 carbonatoms, and with at least two methyl groups on the ring, or bicyclicwhere bicyclic refers to two carbon rings, each ring having between 5-8carbon atoms fused together, substituted with at least two methylgroups, and where R₁ =CH₃, or higher alkyl group, R₂ =H, CH₃, or higheralkyl group, R₃ =H, or CH₃, R₄ and R₅ =H, CH₃, or higher alkyl group.

The invention is also concerned with their manufacture, odorantcompositions which contain said compounds as organoleptic activesubstances as well as the use of said compounds as odorants.

BACKGROUND ART

THF derivatives with a phenyl group at the C-4 position of the THF ringhave been reported in the literature which bear a superficialresemblance to the THF derivatives of this invention. U.S. Pat. No.4,404,127 describes the preparation of the THF derivatives shown below.Some of these compounds are new. The organoleptic properties of thesecompounds also are reported. All the THF derivatives claimed in thispatent are described as fruity honey like, bloomy, or green. None ofthese THF derivatives are characterized as amber. ##STR3##

U.S. Pat. No. 4,549,029 describes the synthesis of novel THF derivativeswith a six membered ring at the C-4 position of the THF ring. Thesubstituent at C-4 on the THF ring has no more than seven carbon atoms.These structures are shown below. ##STR4## These compounds are describedas citrus, fruity, floral, or grapefruit. None of these compounds isdescribed as having an amber odor.

C. Sell, Chemistry & Industry, 516 (1990) discusses the chemistry ofambergris including a discussion of newly synthesized amber chemicals.In addition the Chapter entitled "The Fragrance Of Ambergris" by G.Ohloff in Fragrance Chemistry has a discussion of historical aspectsrelated to ambergris, synthesis of amber chemicals, and structuralstudies. G. Ohloff, Fragrance Chemistry, Ernst Theimer Ed., AcademicPress, New York, 1982. Additionally, a discussion of synthetic amberchemicals appears in G. Frater and D. Lamparsky, Perfumes, Art, Science,& Technology, P. M. Muller and D. Lamparsky Eds. Elsevier AppliedScience, New York, 1991, p. 547. A discussion of structure-odorrelationships in ambergris odorants appears in the same book by G.Ohloff, B. Winter, and C. Fehr at p. 287.

Ambergris is a secretion of the blue sperm whale. It is found in theintestinal tract of the animal. One of the major components of ambergrisis the triterpene ambrein. Ambrein itself is odorless, but as ambrein isbroken down outside the whale, the characteristic ambergris odordevelops. Some of the compounds responsible for the odor of ambergrisare shown below. ##STR5##

The important components in this mixture are the perhydronaphthofuranand the octahydronaphthalenol. These materials are commercially producedand they are shown below. The perhydronaphthofuran is known by varioustradenames. These include Ambrox®, Ambroxan®, and Amberlyn®. ##STR6##The octahydronaphthalenol is known as Ambrinol®. Ambrox is a highlyprized perfume component known for its very fine amber odor and fixativeproperties. It is an expensive perfume chemical. Ambrinol is known forits animal and earthy quality. It is less used but also very expensive.Ambrox was first synthesized by Stoll and Hinder in 1950. M. Stoll andM. Hinder, Helv. Chim. Acta, 33, 1251 (1950); M. Stoll and M. Hinder,Helv. Chim. Acta, 36, 1995 (1953). More recent Syntheses of Ambrox arecompiled in G. Frater and D. Lamparsky, Perfumes, Art, Science &Technology, P. M. Muller and D. Lamparsky Eds. Elsevier Applied Science,New York, 1991, p. 547. Paquette and Maleczka have recently reported ona highly convergent synthesis of 9-epi-Ambrox and a minorperhydronaphthopyran component found in ambergris. R. E. Maleczka and L.A. Paquette, J. Org. Chem., 56, 6538 (1991).

Commercial syntheses of Ambrox start with the plant clary sage (Salviasclarea) in which the diterpene sclareol is present. Sclareol is shownbelow. A degradative pathway involving ##STR7## oxidative cleavage,reduction and cyclization has been developed by various workers. L.Ruzicka, C. F. Seidel, and L. L. Engel, Helv. Chim. Acta, 25, 621(1942); H. R. Schenk, H. Gutmann, O. Jeger, and L. Ruzicka, Helv. Chim.Acta 35, 817 (1952); R. Decorzant, C. Vial, F. Naf, and G. M.Whitesides, Tetrahedron, 43, 1871 (1987); and U.S. Pat. No. 4,798,799.

Ambrinol also has been synthesized by a number of routes. M. Stoll andM. Hinder, Helv. Chim. Acta 38, 1593 (1955); M. Stoll C. F. Seidel, B.Willhalm, and M. Hinder, Helv. Chim. Acta 39, 183 (1956); A. G. Armour,G. Buchi, A. Eschenmoser, and A. Storni, Helv. Chim. Acta 42, 2233(1959) footnote 8; P. Christenson, B. Willis, F. Wehrli, and S. Wehrli,J. Org. Chem., 47, 4786 (1982); and P. Naegeli and Y. Wirz-Habersack,Tetrahedron Asymmetry, 3, 221 (1992). It is the only commercial productavailable from synthetic starting materials, namely(±)-dihydro-Γ-ionone. ##STR8##

All these previous routes to amber chemicals are expensive. There is aneed for cheaper amber chemicals which are more industrially accessible.Vlad reports the preparation of an amber THF derivative shown below. P.F. Vlad, A. F. Morary, and M. N. Koltsa, SU 1169971 (1983) This compoundis a C-2,3 disubstituted ##STR9## tetrahydrofuran with a substituent atC-3 of the THF ring with eleven carbon atoms. This is substantiallydifferent from the compounds claimed in this disclosure.

Sell and coworkers report the preparation and odor properties of some1,3-dioxane derivatives. EP 276 998 A2. Some of these compounds areshown below. They are completely unrelated to the compounds claimedherein. ##STR10##

Another series of amber smelling 1,3-dioxanes are reported in EP 266 648A2. The general structure is shown below. These compounds are notrelated to the compounds claimed herein. ##STR11##

Some spirocyclic THF derivatives have been reported to possess an amberodor. Chodroff and Vazimni report the bicyclic compounds shown below areamber in odor characteristic. U.S. Pat. No. 3,417,107. These spirocyclesare 3-substituted THF derivatives with no other substituents on the THFring. They are completely unrelated to the THF derivatives of thisinvention. ##STR12##

SUMMARY OF THE INVENTION

The invention concerns substituted tetrahydrofurans (THF) andtetrahydropyrans (THP). Many of these compounds have an amber woody odorwhich is of value in the perfumers' art. These derivatives can besynthesized by the processes outlined in the following schemes.

More particularly, the present invention is concerned with novel odorantcompositions which are characterized by a content of tetrahydrofurans(THF) of structures 1 or 2, or tetrahydropyrans of structure 3.##STR13## wherein R can be an acyclic, where acyclic refers to a chainof at least four carbon atoms substituted with at least three methylgroups in the chain, carbocyclic, where carbocyclic refers to a ring of5-8 carbon atoms, and with at least two methyl groups on the ring, orbicyclic where bicyclic refers to two carbon rings, each ring havingbetween 5-8 carbon atoms fused together, substituted with at least twomethyl groups, and where R₁ =CH₃, or higher alkyl group, R₂ =H, CH₃, orhigher alkyl group, R₃ =H, or CH₃, R₄ and R₅ =H, CH₃, or higher alkylgroup.

The invention is also concerned with the novel compounds of structures1-3, their manufacture, odorant compositions which contain saidcompounds as organoleptic active substances as well as the use of saidcompounds as odorants.

In the first process (Method 1), a primary or secondary aldehyde (A=H,CH₃) is treated with an allylic alcohol, allyl and methallyl alcohol aretwo examples, in the presence of an acid catalyst. The acetal so formedis treated with citric acid, with or without a solvent and heated inorder to crack out one mole of allylic alcohol, thus forming an enolether which rearranges via the Claisen reaction to α-allylatedaldehydes. The so formed α-allylated aldehyde which can be formed as amixture of diastereomers is treated with a reducing agent to form analcohol which may be formed as a mixture of diastereomers, which iscyclized with an acid catalyst. The resulting THF or THP derivatives arenovel and can be formed as a mixture of diastereomers. These derivativesmay possess an unexpected amber-woody odor.

In the second process (Method 2) a primary or secondary aldehyde (A=H,CH₃) is treated with an allylic halide under the influence of a strongbase in a suitable solvent. The resulting mixture of oxygen and carbonalkylates is heated at 165°-185° C. for an appropriate amount of timeuntil the oxygen alkylate has rearranged via the Claisen reaction toform the C-allylated product. The α-allylated aldehydes may form as amixture of diastereomers. The so-formed α-allylated aldehyde is nowtreated as in the first process (Method 1); that is, reduction to thealcohol which may form as a mixture of diastereomers and cyclizationwith an acid catalyst to the THF or THP derivative. Again these novelTHF and THP derivatives may form as a mixture of diastereomers.##STR14##

DETAILED DESCRIPTION OF THE INVENTION

The compounds in accordance with the invention comprise tetrahydrofurans(THF) of structures 1 and 2, and tetrahydropyrans of structure 3.##STR15## wherein R can be an acyclic, where acyclic refers to a chainof at least four carbon atoms substituted with at least three methylgroups in the chain, carbocyclic, where carbocyclic refers to a ring of5-8 carbon atoms, and with at least two methyl groups on the ring, orbicyclic where bicyclic refers to two carbon rings, each ring havingbetween 5-8 carbon atoms fused together, substituted with at least twomethyl groups, and where R₁ =CH₃, or higher alkyl group, R₂ =H, CH₃, orhigher alkyl group, R₃ =H, or CH₃, R₄ and R₅ =H, CH₃, or higher alkylgroup.

Tetrahydrofurans of structure 2 are representative of spirocycles whereR can be carbocyclic, with between 5-8 carbon atoms and at least twomethyl groups, or bicyclic with between 5-8 carbon atoms and at leasttwo methyl groups.

By "higher alkyl group" is meant an alkyl group having 2 to 6,preferably 2 to 3, carbon atoms. When substituents R₁ to R₅ are alkyl,they are most preferably methyl or ethyl.

Some of these compounds with R groups shown in Table 1 are characterizedas woody amber. The observation of amber notes is novel and unexpected.The THP derivatives are found to be weaker in odor than the analogousTHF derivatives. These compounds are shown in Table 2. Particularlyuseful are THF compounds where R₁ =H or CH₃ and R₂ =H or CH₃, but R₁ andR₂ are not both H, and R₃ =CH₃ and R₄ =R₅ =H. Also of particular use arespirocycles with R=C₆ and a tert-butyl group in the 3 position, andR=bicyclo[4.1.0]heptanyl system with methyl groups at the 7,7, and 11position.

                                      TABLE 1                                     __________________________________________________________________________     ##STR16##                                                                    R          R.sub.1                                                                          R.sub.2                                                                          R.sub.3                                                                          R.sub.4                                                                          R.sub.5                                                                          Odor Description                                    __________________________________________________________________________     ##STR17## CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                     H CH.sub.3 H H CH.sub.3                                                          H H CH.sub.3 CH.sub.3 CH.sub.3                                                   H H H CH.sub.3 H                                                                 Amber woody Woody Amber Amber Woody Animal                                    Amber Woody Amber Woody Leather Animaile             ##STR18## CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                     H H CH.sub.3 CH.sub.3 CH.sub.3                                                   H H H CH.sub.3 H                                                                 H CH.sub.3 CH.sub.3 H H                                                          H H H H H                                                                        Woody Fruity Woody Fresh Woody Camphoraceous                                  Woody Camphoraceous Weak Amber Woody                 ##STR19## CH.sub.3 CH.sub.3 CH.sub.3                                                       CH.sub.3 CH.sub.3 CH.sub.3                                                       H H CH.sub.3                                                                     H CH.sub.3 H                                                                     H H H                                                                            Citrus Nootkatone Woody Woody Spicy Balsamic                                  Woody Cedar Plastic Vanillin Notes                   ##STR20## CH.sub.3 CH.sub.3                                                                CH.sub.3 CH.sub.3                                                                H H                                                                              H CH.sub.3                                                                       H H                                                                              Amber Woody Labdanum Woody Amber Camphoraceous       ##STR21## CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  Amber Woody Fruity                                   ##STR22## CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  Woody Fruity                                         ##STR23## CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                              CH.sub.3 H CH.sub.3 CH.sub.3                                                     H CH.sub.3 CH.sub.3 H                                                            H H H CH.sub.3                                                                   H H H H                                                                          Amber Woody Woody Amber Woody Amber Amber Dry                                 Tobacco                                              ##STR24## CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                              H H CH.sub.3 CH.sub.3                                                            H CH.sub.3 CH.sub.3 H                                                            H H H H                                                                          H H H H                                                                          Woody Amber Weak Fruity Woody Powdery Amber                                   Woody Sandalwood Woody Fruity                        ##STR25## CH.sub.3                                                                         CH.sub.3                                                                         -- H  H  Woody Amber Camphoraceous                            ##STR26## CH.sub.3 CH.sub.3                                                                H CH.sub.3                                                                       CH.sub.3 CH.sub.3                                                                H H                                                                              H H                                                                              Fresh Woody Amber Clean Decatone Musty               ##STR27## CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  Green Rosey Weak                                     ##STR28## CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  Bell Pepper Green                                    ##STR29## CH.sub.3                                                                         CH.sub.3                                                                         -- H  H  Timberel Woody Amber                                 ##STR30## CH.sub.3 CH.sub.3                                                                CH.sub.3 H                                                                       -- --                                                                            H H                                                                              H H                                                                              Weak Woody Vetiver Fresh Woody Vertinex                                       Cedarwood                                           __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR31##                                                                    R          R.sub.1                                                                              R.sub.2 R.sub.3                                                                            Odor Description                               ______________________________________                                         ##STR32## CH.sub.3 CH.sub.3                                                                    CH.sub.3 CH.sub.3                                                                     H CH.sub.3                                                                         Weak Woody Fresh Spicey Ginger Milkey                                         Green Nootkatone                                ##STR33## CH.sub.3                                                                             CH.sub.3                                                                              H    Weak Woody                                      ##STR34## CH.sub.3                                                                             CH.sub.3                                                                              H    Weak Woody                                      ##STR35## CH.sub.3                                                                             CH.sub.3                                                                              H    Weak Woody                                     ______________________________________                                    

Having regard to their valuable olfactory properties with a very broadspectrum, the compounds of the invention are suitable as odorants,especially in combination with the extensive range of natural andsynthetic odorants which are nowadays available for the creation ofperfume compositions which can be used in all spheres of application.Examples of the numerous known odorant ingredient of natural orsynthetic origin, whereby the range of the natural raw substances canembrace not only readily volatile but also moderately volatile anddifficultly volatile components and that of the synthetics can embracerepresentatives from several classes of substances, are:

Natural products, such as tree moss absolute, basil oil, tropical fruitoils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtleoil, palmarosa oil, patchouli oil, petit grain oil, wormwood oil,lavender oil, rose oil, jasmine oil, ylang-ylang oil, sandalwood oil,

alcohols, such as farnesol, geraniol, linalool, nerol, phenylethylalcohol, rhodinol, cinnamic alcohol, cis-3-hexenol, menthol,α-tocopherol,

aldehydes, such as citral, α-hexylcinnaldehyde, hydroxycitronellal,Lilial (p-tert.butyl-α-methyl-dihydrocinnamaldehyde),methylnonylacetaldehyde, phenylacetaldehyde, anisaldehyde, vanillin,

ketones, such as allylionone, α-ionone, β-ionone, isoraldein(isomethyl-α-ionone), verbenone, nootkaton, geranylacetone,

esters, such as allyl phenoxyacetate, benzyl salicylate, cinnamylpropionate, citronelly acetate, decyl acetate, dimethylbenzylcarbinylacetate, ethyl acetoacetate, ethyl acetylacetate, cis-3-hexenylisobutyrate, linalyl acetate, methyl dihydrojasmonate, styrallylacetate, vetiveryl acetate, benzyl acetate, cis-3-hexenyl salicylate,geranyl acetate, etc.,

lactones, such as γ-undecalactone, δ-decalactone, pentadecan-15-olid,

various components often used in perfumery, such as indole,p-menthane-8-thiol-3-one, methyleugenol, eugenol, anethol.

In their use as odorants the compounds of the invention (or theirmixtures) can be employed in wide limits which in compositions canextend, for example, from about 0.1 (detergents) to about 30 weightpercent (alcoholic solutions) without these values being, however,limiting values, since the experienced perfumer can also achieve effectswith even lower concentrations or can synthesize novel complexes witheven higher dosages. The preferred concentrations vary between about 0.5and about 10 weight percent. The compositions manufactured with thecompounds of the invention can be used for all kinds of perfumedconsumer goods (eau de Cologne, eau de toilette, extracts, lotions,creams, body oils, shampoos, soaps, cleansers, air fresheners, salves,powders, toothpastes, mouth washes, deodorants, detergents, fabricconditioners, tobacco, etc.).

The compounds of the invention can accordingly be used in themanufacture of compositions and--as will be evident from the abovecompilation--a wide range of known odorants or odorant mixtures can beused. In the manufacture of such compositions the known odorants orodorant mixtures enumerated above can be used in a manner known to theperfumer, as follows e.g. from W. A. Poucher, Perfumes, Cosmetics andSoaps 2, 7th edition, Chapman and Hall, London, 1974.

By virtue of their superior olfactory properties the compounds of theinvention are preferably used in luxury perfumery and in compositionsfor cosmetics.

The THF derivatives of this invention are available by two differentprocesses. These two processes are known as method 1 and method 2 andare shown in the figure below. ##STR36## In both processes a primary orsecondary aldehyde can be used as the starting material. Thesealdehydes, where R can be defined as the structures below which in noway limits the choice of the aldehyde, and where A can be defined as ahydrogen atom, or methyl group, are synthesized by well known methodsfound in the chemical literature and known to those who practice theart. The arrow indicates the position of attachment of thecarboxaldehyde group. For example, whereR=2,2,3-trimethyl-3-cyclopenten-1-yl and A=CH₃, the synthesis wouldproceedfrom2,2,3-trimethyl-3-cyclopenten-1-ylacetaldehyde(campholerdcaldehyde).The first step is hydroxymethylation-dehydration. A representativeprocedure is described by Schulte-Elte et al. in U.S. Pat. No.4,610,813. The synthesis is shown in the following diagram. ##STR37##The second step in the synthesis involves hydrogenation using anappropriate catalyst. A representative procedure for this particularreaction and compound is found in EP 0155591 A2.

    ______________________________________                                        Starting Aldehydes                                                             ##STR38##                                                                    R                  A                                                          ______________________________________                                         ##STR39##         H                                                           ##STR40##         CH.sub.3                                                    ##STR41##         H                                                           ##STR42##         CH.sub.3                                                    ##STR43##         H                                                           ##STR44##         CH.sub.3                                                    ##STR45##         --                                                          ##STR46##         H                                                           ##STR47##         CH.sub.3                                                    ##STR48##         H                                                           ##STR49##         --                                                          ##STR50##         --                                                         ______________________________________                                    

In method 1, the aforementioned aldehydes are treated with 2.2-3equivalents of an allylic alcohol, preferably methallyl or allyl alcoholunder the influence of an acid catalyst, where p-toluenesulfonic acid ispreferred, in a suitable solvent such as toluene, xylene, cyclohexane,or heptane, where heptane is preferred. The mixture is heated in orderto form an acetal and distill out the water formed.

The novel acetals so obtained can be isolated by distillation, orpreferably further reacted with a catalytic mount of acid, such asp-toluenesulfonic acid or citric acid, where citric acid is preferred,with or without a solvent. Suitable solvents are heptane, toluene,xylene, or mesitylene. When the theoretical mount of allylic alcohol hasbeen removed the final product is obtained by heating at 165°-200° C.,preferably 165°-175° C.

This final rearrangement is known as a Claisen reaction and it can beconveniently monitored by vapor phase chromatography (VPC). T. Masso, A.Portella, and E. Rus, Perruiner And Flavorist, 15, 39 (1990) andreferences cited therein. The Claisen reaction can take from one toeight hours with three hours usually sufficient.

The so obtained α-allylated aldehydes are novel and some exhibit usefulodor properties. However their major function is as intermediates forthe final products. These new aldehydes are shown in the following tablealong with their odor description. The aldehydes are formed as mixturesof diastereomeric isomers.

    ______________________________________                                        Allylated Aldehydes                                                           Compound              Odor                                                    ______________________________________                                         ##STR51##            Fresh pine Camphoraceous                                 ##STR52##            Wormwood Corps N112                                      ##STR53##            Fruity Fresh Aldehydic green Muget                       ##STR54##            Pine Balesm                                              ##STR55##            Woody Amber                                              ##STR56##            Woody Fruity Camphoraceous                               ##STR57##            Floral Quinoline                                         ##STR58##            Woody Amber                                              ##STR59##            Woody Amber Weak                                         ##STR60##            Fruity                                                   ##STR61##            Fresh Leafy Green                                        ##STR62##            Berry Butyric                                            ##STR63##            Fruity Sweet Raspberry                                   ##STR64##            Weak                                                     ##STR65##            Woody                                                    ##STR66##            Piney woody                                              ##STR67##            Fruity                                                   ##STR68##            Fruity Weak                                              ##STR69##            Camphoraceous                                            ##STR70##            Camphoraceous                                            ##STR71##                                                                    ______________________________________                                    

The α-allylated aldehydes can be reduced to alcohol derivatives by theusual reducing agents. These include lithium aluminum hydride (LAH),sodium borohydride, or aluminum isopropoxide/isopropanol with the latterbeing preferred based on the economy of the reagents. The aforementionedreagents deliver a hydride to the aldehyde; however, alkyl groups C₁ -C₃are readily formed by the addition of methyl, ethyl, or propyl Grignardreagents, or the analogous li-thium reagent. These compounds with R₄ =H,or CH₃, are shown in the following table along with their odordescription. They are novel and are used as intermediates for thesynthesis of the product THF derivatives. The alcohols are formed asmixtures of diastereomeric isomers.

    ______________________________________                                        Alcohols                                                                      Compound              Odor                                                    ______________________________________                                         ##STR72##            Weak woody Amber                                         ##STR73##            Weak                                                     ##STR74##            Amber Woody                                              ##STR75##            Weak Woody                                               ##STR76##            Woody Pine                                               ##STR77##            Earthy woody Musty Cedar                                 ##STR78##            Weak Floral Rosey Honey                                  ##STR79##            Weak Floral                                              ##STR80##            Weak Woody                                               ##STR81##            Weak Fruity                                              ##STR82##            Fresh Fruity Minty spicy Woody                           ##STR83##            Weak                                                     ##STR84##            Weak Woody                                               ##STR85##            Weak                                                     ##STR86##            Weak                                                     ##STR87##            Camphoraceous                                            ##STR88##            Woody                                                    ##STR89##            Weak                                                     ##STR90##            Weak                                                     ##STR91##            Weak                                                     ##STR92##            Weak                                                     ##STR93##                                                                     ##STR94##            Weak                                                     ##STR95##            Weak                                                     ##STR96##                                                                     ##STR97##                                                                    ______________________________________                                    

The cyclization of these alcohols is accomplished by the catalyticaction of p-toluenesulfonic acid, 62% H₂ SO₄, or amberlyst-15. Otheracids also are useable. The solvents appropriate for this cyclizationare pentane, hexane, heptane, or toluene, with hexane and heptane beingespecially preferred. The temperature of the reaction is most easily setat the reflux point of the solvent. The time of the reaction can varybetween 1-24 hours, with 1-5 hours being especially preferred.

A special case is the one where 2,2,3-trimethyl-3-cyclopenten-1-yl isattached to the pentenol fragment. The choice of the acid catalystdetermines the structure of the product. With p-toluenesulfonic acid inhexane, the product is a4-(2,2,3-trimethyl-3-cyclopenten-1-yl)tetrahydrofuran derivative(mixture of diastereomers). Whereas, with amberlyst-15 or other strongprotic acids, in hexane or heptane, the product is a4-(2,3,3-trimethyl-1-cyclopenten-1-yl)tetrahydrofuran derivative.

In the second process (Method 2), a primary or secondary aldehyde (R=H,CH₃) is treated with an allylic halide under the influence of a strongbase in a dipolar aprotic solvent such as dimethylformamide (DMF), ordimethylacetamide (DMA), or tetra methylethylenediamine (TMEDA). DMF isthe most preferred solvent and potassium tert-butoxide is a preferredbase. Potassium tert-amylate, sodium, or potassium amide are alsoacceptable.

The resulting mixture of oxygen and carbon alkylates is heated at 165°C. to 185° C. for an appropriate amount of time, until the oxygenalkylate has converted via the Claisen rearrangement to the carbonalkylated product. This product can be a mixture of diastereomers. Thedetails of the process are shown below. ##STR98##

The so formed α-allylated aldehyde is now treated as in the firstprocess (Method 1); that is, reduction to the alcohol using suchreductants as lithium aluminum hydride, sodium borohydride, or aluminumisopropoxide/isopropanol, or any of a number of other aluminumalkoxides. The alcohol can be obtained as a mixture of diastereomers.The so obtained alcohol is then cyclized to a THF, or THP derivativeusing a suitable acid catalyst. Suitable acid catalysts includep-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, orAmberlyst 15. Suitable solvents for this reaction include pentane,hexane, heptane, toluene or xylene. Hexane and heptane are mostpreferred. The details of this method are shown below. ##STR99##

The odor of many of these THF derivatives are characterized aswoody-amber. The formation of an amber odor is a very desirable element.There are no examples of amber aroma chemicals with the substitutionpattern embodied in this patent application. An amber aroma chemicalthat is inexpensive to produce would be advantageous. Many of theseaforementioned THF derivatives are derived from inexpensive stagmaterials and consequently the product THF or THP derivatives arethemselves inexpensive to produce. THF and THP derivatives in accordancewith the invention are shown in the following tables along with theirodor description.

The following compounds are preferred:2,2,4-trimethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)tetrahydrofuran(mixture of diastereomers),2,2-dimethyl-4-(2,2,3-trimethylcyclopentan-1-yl)tetrahydrofuran (mixtureof diastereomers),2,2-dimethyl-4-(2,3,3-trimethylcyclopentan-1-yl)tetrahydrofuran (mixtureof diastereomers),2,2-dimethyl-4-(3,3-dimethylbicyclo[2.2.1]-heptan-2-yl) tetrahydrofuran(mixture of diastereomers),2,4-dimethyl-4-(3,3-dimethylbicyclo[2.2.1]heptan-2-yl)tetrahydrofuran(mixture of diastereomers),2,2,4-trimethyl-4-(3,3-dimethylbicyclo[2.2.1]-heptan-2-yl)tetrahydrofuran(mixture of diastereomers),2,2,5-trimethyl-4-(3,3-dimethylbicyclo[2.2.1]heptan-2-yl)tetrahydrofuran(mixture of diastereomers),6,8-methano-3,3,7,7,11-pentamethyl-2-oxaspiro[4,5]decane (mixture ofdiastereomers).

The most preferred compounds are:2,2,4-trimethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl) tetrahydrofuran(mixture of diastereomers),2,4-dimethyl-4-(3,3-dimethylbicyclo[2.2.1]heptan-2-yl) tetrahydrofuran(mixture of diastereomers),2,2,4-trimethyl-4-(3,3-dimethylbicyclo[2.2.1]heptan-2-yl)tetrahydrofuran(mixture of diastereomers),6,8-methano-3,3,7,7,11-pentamethyl-2-oxaspiro[4.5]decane (mixture ofdiastereomers).

                                      TABLE 1                                     __________________________________________________________________________     ##STR100##                                                                   R         R.sub.1                                                                          R.sub.2                                                                          R.sub.3                                                                          R.sub.4                                                                          R.sub.5                                                                          Odor Description                                     __________________________________________________________________________     ##STR101##                                                                             CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.8                                     CH.sub.3 CH.sub.9 CH.sub.9 CH.sub.9 CH.sub.8                                     H CH.sub.3 H H CH.sub.8                                                          H H CH.sub.9 CH.sub.9 CH.sub.8                                                   H H H CH.sub.9 H                                                                 Amber woody Woody Amber Amber Woody Animal Amber                              Woody Amber Woody Leather Animalic                    ##STR102##                                                                             CH.sub.9 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                     H H CH.sub.3 CH.sub.3 CH.sub.3                                                   H H H CH.sub.3 H                                                                 H CH.sub.3 CH.sub.3 H H                                                          H H H H H                                                                        Woody Fruity Woody Fresh Woody Camphoraceous                                  Woody Camphoraceous Weak Amber Woody                  ##STR103##                                                                             CH.sub.3 CH.sub.3 CH.sub.3                                                       CH.sub.3 CH.sub.3 CH.sub.3                                                       H H CH.sub.3                                                                     H CH.sub.3 H                                                                     H H H                                                                            Citrus Nootkatone Woody Woody Spicy Balsamic                                  Woody Cedar Plastic Vanillin Notes                    ##STR104##                                                                             CH.sub.3 CH.sub.3                                                                CH.sub.3 CH.sub.3                                                                H H                                                                              H CH.sub.3                                                                       H H                                                                              Amber Woody Labdanum Woody Amber Camphoraceous        ##STR105##                                                                             CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  Amber Woody Fruity                                    ##STR106##                                                                             CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  Woody Fruity                                          ##STR107##                                                                             CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                              CH.sub.3 H CH.sub.3 CH.sub.3                                                     H CH.sub.3 CH.sub.3 H                                                            H H H CH.sub.3                                                                   H H H H                                                                          Amber Woody Woody Amber Woody Amber Amber Dry                                 Tobacco                                               ##STR108##                                                                             CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3                                              H H CH.sub.3 CH.sub.3                                                            H CH.sub.3 CH.sub.3 H                                                            H H H H                                                                          H H H H                                                                          Woody Amber Weak Fruity Woody Powdery Amber                                   Woody Sandalwood Woody Fruity                         ##STR109##                                                                             CH.sub.3                                                                         CH.sub.3                                                                         -- H  H  Woody Amber Camphoraceous                             ##STR110##                                                                             CH.sub.3 CH.sub.9                                                                H CH.sub.9                                                                       CH.sub.3 CH.sub.3                                                                H H                                                                              H H                                                                              Fresh Woody Amber Clean Decatone Musty                ##STR111##                                                                             CH.sub.9                                                                         CH.sub.9                                                                         H  H  H  Green Rosey Weak                                      ##STR112##                                                                             CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  Bell Pepper Green                                     ##STR113##                                                                             CH.sub.3                                                                         CH.sub.3                                                                         -- H  H  Timberol Woody Amber                                  ##STR114##                                                                             CH.sub.3                                                                         CH.sub.3                                                                         -- H  H                                                       __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR115##                                                                   R         R.sub.1 R.sub.2                                                                              R.sub.3                                                                             Odor Description                               ______________________________________                                         ##STR116##                                                                             CH.sub.3 CH.sub.3                                                                     CH.sub.3 CH.sub.3                                                                    H CH.sub.3                                                                          Weak Woody Fresh Spicey Ginger Milkey                                         Green Nootkatone                                ##STR117##                                                                             CH.sub.3                                                                              CH.sub.3                                                                             H     Weak Woody                                      ##STR118##                                                                             CH.sub.3                                                                              CH.sub.3                                                                             H     Weak Woody                                      ##STR119##                                                                             CH.sub.3                                                                              CH.sub.3                                                                             H     Weak Woody                                     ______________________________________                                    

EXAMPLES

¹ H-NMR spectra were obtained in CDCl₃ with (CH₃)₄ Si as an internalstandard.

¹³ C-NMR spectra were obtained in CDCl₃ with (CH₃)₄ Si as an internalstandard.

VPC were run using a J & W 30 m DB-Wax capillary column using helium asthe carrier gas.

EXAMPLE 1 2-(2,2,3-Trimethylcyclopent-3-en-1-yl)-4-methyl-4-pentenal(mixture of diastereomers)

A 2 liter 3 neck flask equipped with a Dean-Stark trap, condenser,thermometer, mechanical agitator, and nitrogen inlet and outlet wascharged with 392.5 g of 2,2,3-trimethylcyclopent-3-en-1-yl acetaldehydeat a purity of 88.9% (2.30 moles), 415 g of 2-methyl-2-propen-1-ol (5.64moles), 0.2 g of p-TSA and 1 liter of heptane. The contents were broughtto reflux and 43 ml of water were collected. The batch was cooled andwashed with 2×250 ml of 10% sodium hydroxide. The batch was dried(MgSO₄), filtered and concentrated in vacuo to yield 671 g of crude2,2,3-trimethylcyclopent-3-en-1-yl acetaldehydebis-(2-methyl-2-propenyl) acetal. BP 88° C./1.0 mmHg; ¹ H-NMR (300 MHz),δ 0.76 (3H, s), 0.98 (3H, s), 1.58 (1H, m), 1.61 (3H, s), 1.76 (6H, s),1.86-2.0 (3H, m), 2.31 (1H, br s), 3.88-4.04 (4H, m), 4.65 (1H, m), 4.87(2H, s), 4.89 (2H, s), 5.22 (1H, s); ¹³ C-NMR (75 MHz), δ 12.74, 19.87,19.91, 25.71, 33.98, 35.88, 46.20, 47.10, 69.00, 69.72, 102.28, 112.27,112.35, 122.36, 142.84, 148.98; IR (Neat), 1130, 1000 cm⁻¹ ; MS (m/e),206 (M⁺ -72), 108 (Base); The crude acetal, with 3 g of citric acidadded, was distilled through a 10" saddle packed column at a pressure of115 mmHg. A total of 185.6 g of lights was distilled out between68°-115° C. The batch was now heated under nitrogen at 160° C. for 3hours. The batch was now distilled to afford 320.1 g of purified product(74% yield). BP 81° C./0.4 mmHg; ¹ H-NMR (300 MHz), δ 0.88 (3H, s), 0.96(3H, s), 1.59 (3H, s), 1.71 (3H, s), 1.9-2.4 (5H, m), 2.65 (1H, m), 4.71(1H, s), 4.76 (1H, s), 5.24 (1H, s), 9.49 (1H, d, J=5.43 Hz); ¹³ C-NMR(75 MHz), δ 12.64, 20.26, 22.67, 26.34, 34.19, 37.57, 47.24, 50.47,52.29, 113.20, 121.39, 143.01, 149.47, 205.82; IR (Neat), 3080, 3050,2950, 2715, 1730, 1655 cm⁻¹ ; MS (m/e), 206 (M⁺), 108 (Base);

Odor: Wormwood Corps N-112

EXAMPLE 2 2-(2,2,3-Trimethylcyclopent-3-en-1-yl)-4-methyl-4-pentenol(mixture of diastereomers)

A 500 ml 3 neck flask was charged with 250 ml of ethanol and 6.0 g ofsodium borohydride (0.16 mole). To the flask maintained at 0° C. in anice bath was added dropwise 74.6 g of the aldehyde from example 1 at apurity of 84.3% (0.30 mole) in 100 ml of ethanol. The batch was stirred45 minutes at 0° C. The reaction was now quenched by the addition of 50ml of 25% hydrochloric acid at 0°-5° C. The mixture was poured onto 300ml of brine and extracted with 3×100 ml of hexane. The hexane was washedwith 2×250 ml of brine, dried with magnesium sulfate, filtered, andconcentrated in vacuo. The batch was distilled through a 10 cm vigreauxcolumn to afford 48 g of purified product (58% yield). BP 78° C./0.25mmHg; ¹ H-NMR (300 MHz), δ 0.91 (3H, s), 1.09 (3H, s), 1.60 (3H, s),1.77 (3H, s), 1.85-2.30 (71-1, m), 3.66 (2H, m), 4.80 (2H, s), 5.24 (1H,s); ¹³ C-NMR (75 MHz), δ 12.90, 20.20, 22.76, 27.36, 34.07, 39.57,40.61, 47.53, 50.32, 64.52, 112.63, 122.26, 146.38, 149.32; IR (Neat),3370, 2960, 2940, 1650, 1040 cm⁻¹ ; MS (m/e), 208 (M⁺), 95 (Base).

EXAMPLE 32,2-Dimethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydrofuran(mixture of diastereomers)

A 500 ml 3 neck round bottomed flask was charged with 56.1 g of2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-methyl-4-pentenol, (0.26 mole),260 ml of hexane, and 0.75 g of p-TSA. The mixture was then refluxed for7 hours. After cooling the batch was washed with 250 ml of 10% sodiumcarbonate, and once with 250 ml of brine. The batch was dried withmagnesium sulfate, filtered, and concentrated in vacuo. The crudeproduct was distilled through a 10 cm micro Vigreaux column to afford49.6 g of purified product (90% yield). BP 51°-52° C./0.2 mmHg; ¹ H-NMR(300 MHz), δ 0.85 (3H, s), 0.95 (3H, s), 1.22 (3H, s), 1.27 (3H, s),1.45 (1H, m), 1.58 (3H, s), 1.73 (1H, m), 1.83-2.0 (2H, m), 2.15 (1H,m), 2.40 (1H, m), 3.46 (1H, m, B part of ABX, J_(AB) =6.63 Hz, J_(BX)=6.63 Hz), 4.07 (1H, t, A part of ABX, J_(AB) =6.63 Hz, J_(AX) =6.63Hz), 5.21 (1H, s), ¹³ C-NMR (75 MHz), δ 12.59, 19.93, 26.57, 28.87,29.09, 35.42, 42.06, 45.82, 47.09, 54.39, 72.08, 79.67, 121.98, 149.07;IR (Neat), 2980, 1055 cm⁻¹ ; MS (m/e), 208 (M⁺), 193, 177, 43 (Base);

Odor: Woody amber

EXAMPLE 4[rac]-2,2-Dimethyl-4-(2,3,3-trimethylcyclopent-1-en-1-yl)tetrahydrofuran

A 250 ml 3 neck round bottomed flask was charged with 12.1 g of thealcohol from Example 2, at 82.7% purity (0.048 mole), 100 ml of heptane,and 1.5 g of Amberlyst-15. The mixture was refluxed under nitrogen for24 hours. After cooling, the Amberlyst-15 was filtered and the batch waswashed with 100 ml of 10% sodium carbonate, and 100 ml of brine. Thebatch was dried over magnesium sulfate, filtered, and concentrated invacuo to afford 12.6 g of crude product. The material was distilled on a10 cm Vigreaux column to afford 8.7 g of purified product (78% yield).BP 58° C./0.40 mmHg; ¹ H-NMR (300 MHz), δ 0.95 (6H, s), 1.25 (3H, s),1.30 (3H, s), 1.53 (3H, s), 1.6 (3H, m), 1.8 (1H, doubled A part of ABspectrum J=8.1 Hz, 12.2 Hz), 2.2 (2H, br m), 3.30 (1H, quintet, C partof ABC system), 3.56 (1H, t, B part of ABC system, J_(AB) =8.0 Hz,J_(BC) =8.0 Hz), 3.85 (1H, t, A part of ABC J_(AB) =8.0 Hz, J_(AC) =8.0Hz) ¹³ C-NMR (75 MHz), δ 9.60, 26.37, 26.81, 28.47, 28.89, 28.95, 38.97,39.39, 43.52, 47.16, 70.42, 81.18, 132.13, 141.57; IR (Neat), 2980,1460, 1050 cm⁻¹ ; MS (m/e), 208 (M⁺), 163 (Base);

Odor: Citrus nootkatone woody

EXAMPLE 5 2-(2,2,3-Trimethylcyclopent-3-en-1-yl)propanal (mixture ofdiastereomers)

A 3 liter 3 neck round bottomed flask was charged with 50 g of sodiumhydroxide (1.25 moles) in 250 g of methanol. 200 g of paraformaldehyde,500 g of hexane and 2.5 g of BHA were added and the flask was cooled to0° C. With fast agitation 500 g of campholenic aldehyde at a purity of88.9% (2.92 moles) were added dropwise over 70 minutes keeping thetemperature at 0°-5° C. The batch was stirred for 3 hours at 0° C. Then50 ml of water was added and the layers are separated. The water layerwas back extracted with 250 ml of hexane. The hexane extracts werecombined and washed with 2×500 ml of 10% sodium hydroxide and 3×500 mlof water. The batch was dried and afforded 1163 g of crude2-(2,2,3-trimethylcyclopent-3-en-1-yl)propenal in hexane. A second batchwas prepared analogously affording 1169 g of crude product.

The batches were hydrogenated separately on a Parr shaker using 10 g of5% Palladium on carbon and 100 ml of 10% sodium carbonate. In this waywere obtained 1064 g of crude product which was distilled from 25 g ofboric anhydride and 1.5 g of BHA to afford 805 g of purified product(81% yield). BP 51° C./0.3 mmHg; ¹ H-NMR (300 MHz), δ 0.93 (3H, s), 1.11(3H, s), 1.16 (3H, d, J=6.8 Hz), 1.59 (3H, s), 1.9-2.6 (4H, m), 5.21(1H, s), 9.64 (1H, d, J=3.3 Hz); ¹³ C-NMR (75 MHz), δ 12.38, 13.92,19.88, 27.12, 33.47, 47.96, 50.84, 51.81, 121.47, 148.30, 204.83; IR(Neat), 2980, 2705, 1725 cm⁻¹ ; MS (m/e), 166 (M⁺), 108 (Base).

EXAMPLE 6 2,4-Dimethyl-2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-pentenal(mixture of diastereomers)

A 4 neck 2 liter round bottomed flask was charged with 600 ml of DMF and160 g of potassium t-butoxide (1.35 moles). Under nitrogen the flask wascooled to 0° C. and 200 g of2-(2,2,3-trimethylcyclopent-3-en-1-yl)propanal (from Example 5) at 90%purity (1.08 moles) in 100 ml of DMF were added over 40 minutes at 0°-5°C. The reaction was stirred 30 minutes at 0° C. Then 140 g of methallylchloride (1.54 moles) in 100 ml of DMF were added dropwise over 40minutes at 5°-15° C. The batch was stirred 30 minutes at 10°-15° C. Withgood stirring the reaction mixture was poured onto 1 liter of water andextracted with 3×100 ml of hexane. The hexane extract was washed with2×500 ml of water and 1 liter of brine. The extract was dried andconcentrated in vacuo. The crude mixture of C- and O-alkylates, 261.4 g,was heated in a 500 ml 3 neck flask under nitrogen at 165° C. for 6.5hours. Fractional distillation afforded 239.5 g of purified product(86.8% yield). BP 84° C./0.15 mmHg; ¹ H-NMR (300 MHz), δ 0.89 (3H, s),1.03 (3H, s), 1.11 (3H, s), 1.55 (3H, s), 1.63 (3H, s), 2.20-2.27 (4H,m), 2.53 (1H, m), 4.67 (1H, s), 4.84 (1H, s), 5.27 (1H, s), 9.79 (1H,s); ¹³ C-NMR (75 MHz), δ 12.34, 15.27, 22.25, 24.31, 28.11, 30.89,46.11, 48.20, 52.83, 56.17, 115.57, 120.98, 141.43, 148.00, 207.01; m(Neat), 2980, 2700, 1725, 1645, 1450, 1380, 895 cm⁻¹ ; MS (m/e), 220(M⁺), 205, 191, 121, 108 (Base), 93, 55, 41;

Odor: Woody amber

EXAMPLE 7 2-(2,2,3-Trimethylcyclopent-3-en-1-yl)-2,4-dimethyl-4-pentenol(mixture of diastereomers)

A 4 neck 1 liter round bottomed flask was charged with 400 g of dryisopropanol and 100 g of aluminum isopropoxide (0.48 mole). The contentsof the flask were refluxed (80° C.) and 200 g of2,4-dimethyl-2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-pentenal at 95.2%(0.865 mole) were added dropwise under nitrogen over 80 minutes. Thereaction was refluxed for 2 hours. Then the lights were distilled off toa pot temperature of 110° C. After cooling the batch was extracted with150 ml of 10% sulfuric acid and 300 ml of hexane. The hexane extract waswashed with 150 ml of water, 100 ml of 5% sodium carbonate, and 100 mlof brine. After drying with magnesium sulfate, the batch was filtered,concentrated in vacuo and the crude alcohol, 201.1 g, was distilled from1 g of soda ash to afford 193.6 g of purified product (88% yield). BP94° C./0.10 mmHg; ¹ H-NMR (300 MHz), δ 1.007 (3H, s), 1.02 (3H, s), 1.42(3H, s), 1.54 (3H, s), 1.83 (4H, br s), 2.0-2.4 (5H, br m), 3.60 (2H, ABquartet, J_(AB) =11.1 Hz), 4.75 (1H, s), 4.88 (1H, s), 5.27 (1H, s); ¹³C-NMR (75 MHz), δ 12.35, 20.07, 22.31, 25.48, 28.38, 30.96, 42.11,45.10, 48.27, 54.77, 68.48, 114.81, 121.38, 144.22, 148.28; IR (Neat),3400 br, 2980, 1040 cm⁻¹ ; MS (m/e), 207 (M⁺ -15), 191, 109 (Base).

EXAMPLE 82,2,4-Trimethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydrofuran(mixture of diastereomers)

A 1 liter 3 neck round bottomed flask was charged with 600 ml ofheptane, 155.3 g of2-(2,2,3-trimethylcyclopent-3-en-1-yl)-2,4-dimethyl-4-pentenol at 97.7%(0.68 mole) and 0.9 g of p-TSA. The batch was refluxed under nitrogenfor 26 hours. Then batch was cooled and washed with 500 ml of 10% sodiumcarbonate, 500 ml of water and 500 ml of brine. The batch was dried withmagnesium sulfate, filtered, and concentrated in vacuo to afford 163.3 gof crude product. Distillation of the product afforded 150.3 g ofpurified product (92.7%). BP 84° C./0.5 mmHg; ¹ H-NMR (300 MHz), δ 0.92(3H, s), 1.10 (3H, s), 1.20 (3H, s), 1.25 (3H, s), 1.33 (3H, s), 1.55(4H, sharp m), 1.81-1.99 (2H, m), 2.16 (2H, br m), 3.60 (2H, AB quintetJ=8.7 Hz), 5.24 (1H, s); ¹³ C-NMR (75 MHz), δ 12.35, 22.03, 24.57,25.66, 28.69, 29.96, 32.48, 47.38, 48.36, 50.58, 57.22, 77.63, 80.60,121.20, 148.01; IR (Neat), 3020, 2980, 1450, 1060 cm⁻¹ ; MS (m/e), 222(M⁺), 207, 191, 95, 43;

Odor: Woody amber musky

EXAMPLE 9 2,2-Dimethyl-4-(2,2,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

42.3 g of2,2-Dimethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydrofuran (fromExample 3), at a purity of 98.7% (0.20 mole) were hydrogenated on a Parrshaker using 1.0 g of 5% Pd on carbon. The crude product, 42.5 g, wasdistilled to afford 41.2 g of purified tetrahydrofuran (98% yield). BP59° C./0.2 mmHg; ¹ H-NMR (300 MHz), δ 0.60 (3H, s), 0.82 (6H, s), 1.20(3H, s), 1.25 (3H, s), 1.2-1.4 (2H, m), 1.6-2.0 (6H, m), 2.25 (1H, m),3.42 (1H, B part of ABX, J_(AB) =7.73 Hz, J_(BX) =7.73 Hz), 4.06 (1H, Apart of ABX, J_(AB) =7.73 Hz, J_(AX) =7.73 Hz); ¹³ C-NMR (75 MHz), δ13.74, 14.84, 26.55, 26.94, 28.10, 29.08, 29.14, 30.18, 42.68, 45.53,45.96, 54.92, 71.90, 79.48; IR (Neat), 2980, 1470, 1050 cm⁻¹ ; MS (m/e),195 (M⁺ -15 Base);

Odor: Amber woody

EXAMPLE 10 2,2-Dimethyl-4-(2,3,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

31.7 g of[rac]-2,2-dimethyl-4-(2,3,3-trimethylcyclopent-1-en-1-yl)tetrahydrofuran(from Example 4), at a purity of 92.7% (0.14 mole) were hydrogenated ona Parr shaker using 2.0 g of 5% Pd on carbon in 50 ml of ethanol. Theproduct, 31.6 g, was distilled to afford 30 g (100% yield). BP 52°-54°C./0.2 mmHg; ¹ H-NMR (300 MHz), δ 0.74 (3H, s), 0.85 (3H, d, J=6.9 Hz),0.94 (3H, s), 1.2 (1H, m), 1.19 (3H, s), 1.28 (3H, s), 1.3-1.6 (5H, m),1.65-1.95 (2H, m), 2.33 (1H, m), 3.47 (1H, m), 3.94 (1H, m); ¹³ C-NMR(75 MHz), δ 13.83, 22.07, 26.75, 28.29, 28.56, 28.82, 40.64, 43.57,44.72, 45.76, 49.56, 49.69, 71.84, 81.25; IR (Neat), 2980, 1460, 1055cm⁻¹ ; MS (m/e), 195 (M⁺ -15), 137, 43 (Base);

Odor: Amber woody labdanum

EXAMPLE 11 3-(2,2,3-Trimethylcyclopent-3-en-1-yl)-5-methyl-5-hexen-2-ol(mixture of diastereomers)

A 500 ml 3 neck round bottomed flask was charged with 27.3 g of4-methyl-2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-pentenal (fromExample 1) (0.127 mole) in 150 ml of dry ether. The flask was cooled to0° C. and 55 ml of 3.0M methylmagnesium bromide (0.165 mole) was addedover 30 minutes and stirred 30 minutes at 5° C. The reaction wasquenched by the addition of 100 ml of saturated ammonium chloride. Thelayers were separated and the aqueous was extracted with 2×50 ml ofether. The organic extracts were combined, washed with 200 ml of brine,dried, filtered, and concentrated in vacuo to afford 28.6 g of crudealcohol. Distillation afforded 18.1 g of product (64% yield). BP 88°C./0.3 mmHg; ¹ H-NMR (300 MHz), δ 0.87 (3H, s), 1.00 (3H, s), 1.21 (3H,d, J=8.91 Hz), 1.60 (3H, br s), 1.60 (1H, m), 1.79 (3H, s), 1.82-2.27(6H, m), 4.00 (1H, m), 4.70 (2H, m), 5.27 (1H, S); 13C-NMR (75 MHz), δ12.70, 20.11, 22.42, 26.24, 33.19, 36.88, 37.78, 40.66, 47.51, 49.43,70.11, 112.53, 122.60, 146.92, 148.23; IR (Neat), 3400, 2980, 1650,1140, 1080 cm⁻¹ ; MS (m/e), 222 (M⁺), 43 (Base);

Odor: Woody amber weak

EXAMPLE 122,2,5-Trimethyl-4-(2,3,3-trimethylcyclopent-1-en-1-yl)tetrahydrofuran(mixture of diastereomers)

A 125 ml 3 neck flask was charged with 7.0 g of the alcohol in Example11 (0.03 mole), 75 ml of heptane and 0.7 g of Amberlyst-15. The mixturewas refluxed for 24 hours. After cooling and filtration of theAmberlyst-15, the batch was washed with 100 ml of 10% sodium carbonate,and 100 ml of brine. The batch was dried, filtered, and concentrated invacuo to afford 7.5 g of product. The crude product was distilled toafford 5.2 g of purified product (74.3% yield). BP 54° C./0.1 mmHg; ¹H-NMR (300 MHz), δ 0.97 (6H, s), 1.12 (3H, d, J=5.14 Hz), 1.28 (3H, s),1.29 (3H, s), 1.54 (3H, s), 1.57 (2H, m), 1.77 (2H, d, J=9.57 Hz), 2.18(2H, br m), 2.7 (1H, m), 3.81 (1H, m); ¹³ C-NMR (75 MHz), δ 9.67, 26.15,26.54, 29.87, 30.01, 30.15, 39.90, 44.17, 46.96, 47.16, 77.36, 79.72,131.32, 142.52; IR (Neat), 2980, 1460, 1095 cm⁻¹ ; MS (m/e), 222 (M⁺),163 (Base);

Odor: Woody spicy balsamic

EXAMPLE 132,2,5-Trimethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydrofuran(mixture of diastereomers)

A 500 ml 3 neck flask was charged with 58.8 g of the alcohol fromExample 11 at 91.2% (0.24 mole), 250 ml of hexane, and 0.7 g of p-TSA.The mixture was refluxed for 12 hours. After cooling the mixture waswashed with 250 ml of 10% sodium carbonate, and 250 ml of brine. Themixture was dried with sodium sulfate, filtered, and concentrated invacuo to afford 57.1 g of crude product which was distilled to afford47.9 g of product (90% yield). BP 61° C./0.05 mmHg; ¹ H-NMR (300 MHz), acomplex mixture of at least 3 diastereomers. Spectra consistent withassigned structures; ¹³ C-NMR (75 MHz), spectra consistent with complexmixture of at least 3 diastereomers; IR (Neat), 2980, 1460, 1100, 1080cm⁻¹ ; MS (m/e), 222 (M⁺);

Odor: Amber woody animal

EXAMPLE 142,2,5-Trimethyl-4-(2,2,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

The tetrahydrofuran mixture from Example 13, 35.5 g at 96.7% (0.154mole) was hydrogenated at 60 psi at 40-50° C. using 0.75 g of 5% Pd oncarbon. The crude product, 35.7 g, was distilled to yield 34.4 g ofpurified product (100% yield). BP 53° C./0.04 mmHg; ¹ H-NMR (300 MHz),spectra consistent with assigned structures. ¹³ C-NMR (75 MHz), spectraconsistent with assigned structures. IR (Neat), 2990, 1490, 1130, 1110cm⁻¹ ; MS (m/e), 209 (M⁺ -15), 110, 96 (Base);

Odor: Woody camphoraceous

EXAMPLE 152,2,5-Trimethyl-4-(2,3,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

The mixture of tetrahydrofurans from Example 12, 19.8 g (0.09 mole) washydrogenated with 0.5 g of 5% Pd on carbon in acetic acid at 100°-110°C. The resulting crude product, 16.9 g, was distilled affording 14.8 gof a mixture of tetrahydrofurans (74% yield). BP 72° C./0.30 mmHg; ¹H-NMR (300 MHz), spectra consistent with assigned structures; ¹³ C-NMR(75 MHz), spectra consistent with assigned structures; IR (Neat), 2980,1460, 1080 cm⁻¹ ; MS (m/e), 209 (M⁺ -15), 191, 110, 96, 43 (Base);

Odor: Woody amber camphoraceous

EXAMPLE 163,5-Dimethyl-3-(2,2,3-trimethylcyclopent-3-en-1-yl)-5-hexen-2-ol(mixture of diastereomers)

Similar to Example 11, 11.7 g of2,4-dimethyl-2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-pentenal (fromExample 6), at 94% (0.05 mole) was treated with 30 ml of 3.0Mmethylmagnesium bromide (0.09 mole). This afforded 12.2 g of crudealcohol (>95% yield). BP 110° C./0.1 mmHg (Kugelrohr); ¹ H-NMR (300MHz), δ 1.02 (3H, s), 1.12-1.2 (9H, multiple s), 1.55 (3H, s), 1.87 (3H,multiple s), 2.2-2.6 (6H, m), 3.7-4.0 (1H, m), 4.86 (2H, m), 5.2 (1H,multiple s); ¹³ -NMR (75 MHz), δ 12.35, 18.03, 19.58, 22.76, 25.32,28.79, 31.09, 41.62, 44.56, 48.88, 54.46, 74.54, 115.06, 122.05, 145.27,148.19; IR (Neat), 3500, 2980, 1640, 1450, 1080, 900 cm⁻¹ ; MS (m/e),236 (M⁺), 221, 108 (Base).

EXAMPLE 172,2,4,5-Tetramethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 13, 10.7 g of the alcohol from Example 16 at 95.7%(0.045 mole), 70 ml of hexane, and 0.2 g of p-TSA were refluxed undernitrogen for 7 hours. The usual work-up afforded 10.6 g of crudeproduct. The crude product was distilled to afford 8.9 g of purifiedproduct (87% yield). BP 62° C./0.1 mmHg; ¹ H-NMR (300 MHz), spectraconsistent with assigned structures; ¹³ -NMR (75 MHz), spectraconsistent with assigned structures; IR (Neat), 2980, 1455, 1120, 1110cm⁻¹ ; MS (m/e), 236 (M⁺), 221, 191, 177, 108 (Base);

Odor: Amber woody leather animalic

EXAMPLE 18 2-(2,2,3-trimethylcyclopent-1-yl) acetaldehyde

510 g of 2-(2,2,3-trimethylcyclopent-3-en-1-yl) acetaldehyde at 85%(2.85 moles) were hydrogenated with 20 g of 5% Pd on carbon (50% wet)with 10 g of soda ash at 60 psi and 50°-60° C. The crude product wasdistilled from 22 g of boric anhydride affording 324 g of purifiedproduct, containing pinocamphone as a 10-15% impurity. BP 48° C./0.6mmHg; ¹ H-NMR (300 MHz), δ 0.54 (3H, s), 0.87 (3H, d, J=6.6 Hz), 0.88(3H, s), 1.1-1.4 (2H, m), 2.25 (1H, m), 2.50 (1H, m), 2.55 (1H, m),2.70-2.95 (3H, br m), 9.76 (1H, br s); ¹³ C-NMR (75 MHz), δ 14.01,14.73, 25.54, 28.34, 30.35, 42.62, 44.84, 45.03, 45.75, 203.83; IR(Neat), 2980, 2720, 1730, 1470, 1390, 1370 cm⁻¹ ; MS (m/e), 139 (M⁺-15), 97, 69 (Base).

EXAMPLE 19 2,2,3-Trimethylcyclopent-1-yl acetaldehyde-bis-(2-propenylacetal)

In a similar procedure as in Example 1, 75.5 g of2,2,3-trimethylcyclopent-1-yl acetaldehyde (from Example 18) at 84.4%(0.41 mole), 52 g of allyl alcohol (0.9 mole), 250 ml of heptane and0.25 g of p-TSA were combined and refluxed until water ceasesdistilling. The product was cooled, washed with 100 ml of 10% sodiumcarbonate, dried, filtered, and concentrated. The crude product wasdistilled from 2 g of soda ash affording 69 g of product acetal (66%yield). BP 74° C./0.05 mmHg; ¹ H-NMR (300 MHz), δ 0.51 (3H, s), 0.82(3H, d, J=6.84 Hz), 0.87 (3H, s), 1.2-1.6 (5H, m), 1.81 (3H, m), 4.0(4H, m), 4.6 (1H, dd, J=3.9, 7.95 MHz), 5.16 (2H_(A), d, J_(AX) =10.3Hz), 5.30 (2H_(B), dd, J_(BX) =16.9 Hz, J_(AB) =1.71), 5.9 (2H, m); ¹³C-NMR (75 MHz), δ 13.98, 14.48, 25.59, 28.38, 30.44, 34.42, 42.56,44.99, 46.48, 65.53, 66.83, 102.21, 116.93, 117.01, 135.38, 135.42; IR(Neat), 2960, 1650, 1470, 1125, 1040, 1000, 920 cm⁻¹ ; MS (m/e), 195 (M⁺-57);

Odor: Weak fatty

EXAMPLE 20 2-(2,2,3-Trimethylcyclopent-1-yl)-4-pentenal (mixture ofdiastereomers)

A 125 ml 3 neck flask was charged with 60.1 g of the acetal at 82.9%(0.198 mole) from Example 19, and 1.0 g of citric acid. The flask washeated under nitrogen to a pot temperature of 200° C. when 14.5 ml (12.2g) of allyl alcohol distills off. The batch was now heated at 150° C.for 2 hours. The crude aldehyde, 47.6 g, was distilled to afford 35.2 gof purified product (92%). BP 75° C./0.2 mmHg; ¹ H-NMR (300 MHz), δ 0.62(3H, s), 0.82 (3H, d, J=6.72 Hz), 0.84 (3H, s), 1.2-1.9 (6H, m), 2.3(2H, br s), 2.43 (1H, br s), 5.04 (2H, m), 5.7 (1H, m), 9.5 (1H, s); ¹³C-NMR (75 MHz), δ 13.69, 14.90, 26.47, 29.43, 33.42, 42.69, 45.63,50.49, 52.93, 54.64, 117.51, 135.40, 206.36; IR (Neat), 2980, 2705,1730, 1420 cm⁻¹ ; MS (m/e), 194 (M⁺), 179, 152, 137, 109, 69 (Base);

Odor: Pine balsamic

EXAMPLE 21 2-(2,2,3-Trimethylcyclopent-1-yl)4-pentenol (mixture ofdiastereomers)

Similar to Example 2, 30.0 g of the aldehyde from Example 20, at 94.6%(0.146 mole), 2.7 g of sodium borohydride (0.071 mole) and 100 ml ofethanol give in the usual manner 29.2 g of crude alcohol which affordedafter distillation 23.5 g of purified product (82% yield). BP 72°C./0.18 mmHg; ¹ H-NMR (300 MHz, δ 0.62 (3H, s), 0.82 (3H, d, J=6.78 Hz),0.96 (3H, s), 1.1-1.9 (8H, m), 2.0-2.3 (2H, m), 3.5-3.75 (2H, m), 5.05(2H, m), 5.91 (1H, m); ¹³ C-NMR (75 MHz), δ 13.83, 14.77, 26.15, 26.93,29.82, 34.32, 41.83, 42.70, 45.80, 50.29, 64.23, 116.42, 138.10; IR(Neat), 3350, 2980, 1640, 1470, 1370, 1045, 910 cm⁻¹ ; MS (m/e), 178 (M⁺-16), 163, 109, 69 (Base);

Odor: Weak woody

EXAMPLE 22 2-Methyl-4-(2,2,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Examples 4, 15.4 g of the alcohol from Example 21 at 95.9%(0.075 mole), 75 ml of heptane, and 1.0 g of Amberlyst-15, were chargedto a flask and refluxed for 4 hours. After the usual work-up the crudeproduct, 17.0 g, was distilled affording 11.5 g of pure product (78%);BP 48° C./0.04 mmHg; ¹ H-NMR (300 MHz), δ 0.60 (3H, s), 0.80 (3H, d,J=6.84 Hz), 0.83 (3H, s), 1.21 (3H, d, J=5.97 MHz), 1.1-1.85 (7H, m),2.2 (2H, m), 3.2-3.5 (1H, m), 4.0 (2H, m); ¹³ C-NMR (75 MHz), δ 13.78,14.85, 21.32, 26.86, 28.08, 30.18, 39.17, 41.44, 43.33, 46.53, 55.08,72.02, 74.74; IR (Neat), 2980, 1470, 1370, 1100, 1050, 1020 cm⁻¹ ; MS(m/e), 196 (M⁺), 181, 41 (Base);

Odor: Woody fruity

EXAMPLE 23 3-(2,2,3-Trimethylcyclopent-1-yl)-5-hexen-2-ol (mixture ofdiastereomers)

Similar to Example 11, 76.5 g of the aldehyde from Example 20 at 90%purity (0.355 mole) in 250 ml of dry ether was treated with 130 ml of3.0M methylmagnesium bromide (0.39 mole). This afforded after work-up80.5 g of crude alcohol. Distillation from 2 g of soda ash afforded 69 gof purified alcohol (93% yield). BP 84° C./0.1 mmHg; ¹ H-NMR (300 MHz),spectra consistent with assigned structures, ¹³ C-NMR (75 MHz), δ 13.94,15.32, 20.55, 24.72, 26.30, 29.60, 32.14, 33.52, 43.11, 44.75, 48.67,69.31, 115.41, 139.25; IR (Neat), 3380, 2980, 1640, 1470, 1370, 910 cm⁻¹; MS (m/e), 195 (M⁺ -15), 177, 123, 109, 69 (Base);

Odor: Woody pine

EXAMPLE 24 2,5-Dimethyl-3-(2,2,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 37.4 g of the alcohol from Example 23 at 90%purity (0.16 mole) was treated with 2.0 g of Amberlyst-15, in 250 ml ofheptane. After 2 hours at reflux, the reaction was complete. The usualwork-up afforded 40 g of crude product which was distilled to afford30.3 g of purified tetrahydrofuran (91% yield). BP: 50° C./0.1 mmHg; ¹H-NMR (300 MHz) spectra consistent with assigned structures; ¹³ C-NMR(75 MHz) spectra consistent with assigned structures; IR (Neat), 2980,1460, 1380, 1100, 1070 cm⁻¹ ; MS (m/e), 210 (M⁺), 195, 166, 151, 124,109, 82 (Base);

Odor: Woody fresh

EXAMPLE 25 3-(2,2,3-Trimethylcyclopent-3-en-1-yl)-5-methyl-5-hexen-2-one(mixture of diastereomers)

The alcohol from Example 11, 74.6 g at 90.8% purity (0.31 mole) wasadded at 0° C. to a mixture of 150 g pyridinium chlorochromate (0.522mole) in 1000 ml of methylene chloride. The mixture was stirred for 3hours at room temperature. Ether, 600 ml, was added and the reactionmixture was stirred for 15 minutes. The organics were decanted from theresidue and were filtered through a pad of florisil. The solvents wereremoved in vacuo and the residue, 67.0 g, was distilled to afford 55 gof product (82% yield). BP 85° C./0.3 mmHg; ¹ H-NMR (300 MHz), δ 0.87(3H, s), 0.92 (3H, s), 1.58 (3H, s), 1.73 (3H, s), 2.11 (3H, s), 2.0-2.3(5H, m), 2.85 (1H, m), 4.68 (1H, s), 4.75 (1H, s), 5.24 (1H, s); ¹³C-NMR (75 MHz), δ 13.10, 19.97, 22.60, 26.40, 28.18, 34.51, 40.50,47.56, 52.31, 53.76, 113.07, 121.36, 143.43, 149.39, 212.95; IR (Neat),2960, 2940, 1710, 1650, 1465, 1365, 900 cm⁻¹ ; MS (m/e), 220 (M⁺), 205,177, 108 (Base);

Odor: Woody nootkatone weak citrus

EXAMPLE 262,5-Dimethyl-3-(2,2,3-trimethylcyclopent-3-en-1-yl)-5-hexen-2-ol(mixture of diastereomers)

Similar to Example 11, a 500 ml 3 neck flask was charged with 46.5 g ofthe ketone from Example 25 at 87.4% purity (0.184 mole) in 250 ml of dryether. 75 ml of 3.0M methylmagnesium bromide (0.225 mole) were addeddropwise. After refluxing for 2 hours, work-up of the reaction in theusual manner afforded 46.6 g of crude alcohol (57.4% alcohol, 27%ketone). Distillation afforded 17.0 g of purified alcohol (39% yield).BP 75° C./0.15 mmHg; ¹ H-NMR (300 MHz), δ 0.87 (3H, s), 1.03 (3H, s),1.19 (3H, s), 1.24 (3H, s), 1.61 (3H, s), 1.87 (3H, s), 1.9-2.4 (7H, m),4.81 (1H, s), 4.89 (1H, s), 5.27 (1H, s); ¹³ C-NMR (75 MHz), δ 13.19,21.19, 23.14, 26.39, 26.45, 29.91, 31.83, 38.04, 44.05, 48.84, 50.72,76.52, 111.65, 122.63, 147.71, 149.63; IR (Neat), 3470, 2970, 1650,1470, 1380, 1120, 890 cm⁻¹ ; MS (m/e), 236 (M⁺), 221, 178, 163, 59(Base).

EXAMPLE 272,2,5,5-Tetramethyl-3-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydrofuran

The alcohol from Example 26, 16.6 g at 87.2% purity (0.061 mole), 0.1 gof p-TSA and 100 ml of hexane were heated at 55° C. for approximately 2hours. The reaction was cooled and worked up as usual to afford 16.7 gof crude product. The product was distilled to afford 12.2 g (85% yield)of purified tetrahydrofuran. BP 72° C./0.3 mmHg; ¹ H-NMR (300 MHz), δ0.79 (3H, s), 1.00 (3H, s), 1.02 (3H, s), 1.21 (3H, s), 1.24 (3H, s),1.30 (3H, s), 1.62 (3H, s), 1.70-1.95 (3H, m), 2.09 (3H, m), 5.28 (1H,s); ¹³ C-NMR (75 MHz), δ 12.73, 20.10, 24.68, 24.99, 28.95, 30.20,30.84, 32.16, 42.08, 46.82, 47.90, 48.89, 77.96, 83.21, 122.05, 147.68;IR (Neat), 2980, 1470, 1370, 1135, 990 cm⁻¹ ; MS (m/e), 221 (M⁺ -15),178, 163, 134, 121, 108 (Base);

Odor: Amber woody

EXAMPLE 28 2-(2,2,3-Trimethylcyclopent-1-yl)propanal (mixture ofdiastereomers)

The aldehyde from Example 5, 190 g at 86% purity (0.98 mole) washydrogenated on a Parr shaker at 60 psi and 70° C. using a total of 8.5g of 5% Pd on carbon. The crude product, 180 g, was distilled to afford144 g of purified product (87% yield). BP 53° C./0.6 mmHg; ¹ H-NMR (300MHz), δ 0.64 (3H, s), 0.85 (3H, d, J=6.3 Hz), 1.02 (3H, s), 1.15 (3H, d,J=6.8 Hz), 1.2-1.8 (6H, m), 2.4 (1H, m), 9.61 (1H, s); ¹³ C-NMR (75MHz), δ 13.72, 14.82, 25.89, 26.48, 27.22, 29.34, 29.99, 45.42, 48.79,51.80, 205.22; IR (Neat), 2980, 2700, 1730, 1470 cm⁻¹ ; MS (m/e), 168(M⁺), 153, 111, 69 (Base);

Odor: Camphor borneol

EXAMPLE 29 2,4-Dimethyl-2-(2,2,3-trimethylcyclopent-1-yl)-4-pentenal(mixture of diastereomers)

A 1 liter 3 neck flask equipped with a Dean-Stark trap, mechanicalagitator, condenser, thermometer and nitrogen sweep was charged with thealdehyde from Example 28, 122.9 g at approximately 90% purity (0.66mole), 230 g of methallyl alcohol (3.20 moles), 1.0 g of p-TSA, and 500ml of cyclohexane. The contents were refluxed for 72 hours taking off awater-methallyl alcohol distillate (18 ml). The batch was cooled, washedwith 250 ml of 10% sodium carbonate and 250 ml of brine. The mixture wasdried, filtered, and concentrated in vacuo to afford 311 g of a mixtureof acetal, and starting material. Distillation from 2 g of soda ashafforded 119 g of starting aldehyde. The pot residue 134.8 g containsthe crude acetal (IR (Neat), 2980, 1660, 1470, 1150, 1100 cm⁻¹) whichwas taken up in 200 ml of tetraglyme and 3 g of citric acid. Undernitrogen the flask was heated to 185° C. and 4 ml of methallyl alcoholwere collected (approximately 2.5 hours). The flask was cooled and thecontents were poured into 500 ml of 10% sodium carbonate and extractedwith 2×200 ml of ether. The ether was washed with 200 ml of 10% sodiumcarbonate, 250 ml of water, and 250 ml of brine. The batch was dried,filtered, and concentrated to afford 124.7 g of crude product.Distillation afforded 58 g of purified product (40% yield). BP 2° C./0.3mmHg; ¹ H-NMR (300 MHz), δ 0.64 (3H, s), 0.78 (3H, d, J=6.78 Hz), 0.91(3H, s), 1.05 (3H, s), 1.60 (3H, s), 1.5-1.9 (6H, m), 2.3 (2H, ABquartet, J_(AB) =13.8 Hz), 4.63 (1H, s), 4.81 (1H, s), 9.73 (1H, s); ¹³C-NMR (75 MHz), δ 13.50, 14.67, 16.73, 23.34, 24.23, 27.84, 28.88,44.24, 45.95, 46.32, 53.13, 56.56, 115.46, 141.53, 207.14; IR (Neat),2980, 2700, 1720, 1460, 900 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 166, 123,109, 95, 41 (Base);

Odor: Woody fruity camphoraceous

EXAMPLE 30 2,4-Dimethyl-2-(2,2,3-trimethylcyclopent-1-yl)-4-pentenol(mixture of diastereomers)

Similar to Example 2, 32.0 g of the aldehyde from Example 29 at 64%purity (0.09 mole), 4.0 g of sodium borohydride (0.10 mole) and 100 mlof ethanol were reacted in the usual way. The crude product, 31.5 g, wasdistilled to afford 16.2 g of purified alcohol (79% yield). BP 105°C./0.4 mmHg; ¹ H-NMR (300 MHz), δ 0.73 (3H, s), 0.76 (3H, s), 0.99 (3H,d, J=5.8 Hz), 1.04 (3H, s), 1.15-1.7 (7H, m), 1.82 (3H, s), 2.1-2.35(2H, m), 3.6 (2H_(AB), AB quartet, J=12 Hz), 4.74 (1H, s), 4.88 (1H, s);¹³ C-NMR (75 MHz), δ 13.50, 16.89, 19.82, 23.20, 25.49, 28.49, 29.35,43.43, 45.01, 45.05, 46.33, 54.46, 68.58, 114.68, 144.26; IR (Neat),3400, 2980, 1640, 1470, 1370, 1050, 890 cm⁻¹ ; MS (m/e), 209 (M⁺ -15),193, 168, 151, 43 (Base).

EXAMPLE 312,2,4-Trimethyl-4-(2,2,3-trimethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

In a manner similar to Example 4, 15.5 g of the alcohol from Example 30at 87.5% (0.06 mole), 1.0 g of Amberlyst-15, and 75 ml of hexane wererefluxed for 1 hour. The usual work-up afforded 15.5 g of crude product.The crude tetrahydrofuran was distilled to afford 12.3 g of purifiedproduct (91% yield). BP 85° C./0.5 mmHg; ¹ H-NMR (300 MHz), δ 0.65 (3H,s), 0.78 (3H, d, J=6.78 Hz), 0.98 (3H, s), 1.18 (3H, s), 1.21 (3H, s),1.32 (3H, s), 1.5-2.0 (8H, m), 3.55 (2H_(AB), AB quartet, J_(AB) =8.34Hz); ¹³ C-NMR (75 MHz), δ 13.46, 16.49, 24.56, 25.51, 28.31, 28.64,29.78, 29.90, 43.66, 45.92, 47.68, 50.90, 57.46, 77.79, 80.43; IR(Neat), 2980, 1460, 1370, 1060 cm⁻¹ ; MS (m/e), 209 (M⁺ -15), 191, 168,151, 95, 43 (Base);

Odor: Woody camphoraceous weak

EXAMPLE 32[rac]-2,2,4-Trimethyl-4-(2,3,3-trimethylcyclopent-1-en-1-yl)tetrahydrofuran

The tetrahydrofuran from Example 8, 14.3 g at 88.7% purity (0.057 mole),65 ml of heptane, and 3.5 g of Amberlyst-15 were refluxed under nitrogenfor 48 hours. After cooling the Amberlyst-15 was filtered and theorganic layer was washed with 100 ml of 10% sodium carbonate and 100 mlof brine. The batch was dried, filtered and concentrated in vacuo toafford 11.1 g of crude product. The product was distilled to afford 7.4g of purified product (59% yield). BP 59° C./0.3 mmHg; ¹ H-NMR (300MHz), δ 0.94 (3H, s), 0.95 (3H, s), 1.20 (6H, s), 1.32 (3H, s), 1.52(3H, s), 1.57 (2H, m), 1.9 (2H_(AB), AB quartet, J=12.4 Hz), 2.2 (2H,m), 3.7 (2H, AB quartet, J=8.5 Hz); ¹³ C-NMR (75 MHz), δ 10.93, 25.73,26.22, 26.33, 28.80, 30.02, 31.10, 38.81, 45.96, 47.26, 51.80, 76.50,80.07, 138.19, 138.41; IR (Neat), 2980, 1460, 1370, 1060 cm⁻¹ ; MS(m/e), 222 (M⁺), 207, 191, 177, 149, 135, 121 (Base), 108, 107, 43;

Odor: Woody cedar plastic vanillin notes

EXAMPLE 332,2,4-Trimethyl-4-(1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)tetrahydrofuran(mixture of diastereomers)

This example was an application of the procedure given by E. C.Friedrich, S. E. Lumetta, and E. J. Lewis, J. Org. Chem., 54, 2388(1989).

A 500 ml 4 neck round bottomed flask fitted with a spiral condenser,mechanical agitator, nitrogen inlet, thermometer, rubber septum, and 125ml pressure equalizing dropping funnel was charged with 44.1 g of zincdust (0.67 g atom), 6.68 g of copper (I) chloride (0.067 mole), 120 mlof dry ether, 91.5 g (36.9 ml) of dibromomethane (0.526 mole), and 40.8g of the tetrahydrofuran from Example 8 at a purity of 96% (0.176 mole).Anhydrous titanium (IV) chloride, 2.0 g, (1.12 ml) was added dropwisevia syringe through the rubber septum. After the addition the flask washeated at 45° C. for 24 hours, replacing any ether that evaporates usingthe dropping funnel. The reaction was cooled and carefully poured withstirring into 100 ml of sat. ammonium chloride. Any solids were filteredand the supernatant was washed with 3×100 ml of 10% sodium hydroxide and100 ml of brine. The organics were dried with magnesium sulfate,filtered, and concentrated in vacuo. The crude product, 8.3 g, was amixture of 53.4% product and 43.3% starting material. The mixture wasseparated on a spinning band column to afford 17.0 g of purified product(41% yield). The product was a mixture of two diastereomers 75.4:24.6.BP 60° C./0.08 mmHg; ¹ H-NMR (300 MHz), δ 0.01 (1H, dd, J=7.68, 4.65Hz), 0.43 (1H, dd, J=8.19, 3.99 Hz), 0.88 (3H, s), 0.99 (3H, s), 1.02(3H, s), 1.04 (1H, m), 1.17 (3H, s), 1.18 (3H, s), 1.24 (1H, m), 1.31(3H, s), 1.47-1.82 (4H, m), 3.40 (2H_(AB), AB quartet, J_(AB) =8.64 Hz);¹³ C-NMR (75 MHz), δ 14.44, 17.31, 21.80, 21.99, 25.60, 26.27, 28.42,28.93, 29.95, 32.04, 42.53, 46.68, 51.03, 52.28, 77.55, 80.72; IR(Neat), 2980, 1460, 1370, 1060 cm⁻¹ ; MS (m/e), 236 (M⁺), 221, 205, 123,107, 95, 43 (Base);

Odor: Amber fruity woody

EXAMPLE 342,2,4-Trimethyl-4-(2,2,3,3-tetramethylcyclopent-1-yl)tetrahydrofuran(mixture of diastereomers)

The tetrahydrofuran from Example 33, 12.8 g at 96.7% purity (0.052mole), 0.5 g of platinum oxide and 50 ml of acetic acid was hydrogenatedon a Parr shaker at 55° C. The resulting crude product, 13.5 g, wasdistilled to afford 11.7 g of purified product (95% yield). BP 69°C./0.08 mmHg; ¹ H-NMR (300 MHz), δ 0.76 (3H, s), 0.81 (3H, s), 0.85 (3H,s), 0.91 (3H, s), 1.20 (6H, s), 1.33 (3H, s), 1.38 (1H, m), 1.46-1.81(5H, m), 1.94 (1H, m), 3.50 (2H_(AB), AB quartet, J_(AB) =8.52 Hz); ¹³C-NMR (75 MHz), δ 20.91, 23.04, 23.92, 24.74, 24.98, 26.49, 28.45,30.11, 37.47, 44.89, 45.59, 47.86, 49.73, 53.44, 77.94, 80.78; IR(Neat), 2980, 1470, 1370, 1060 cm⁻¹ ; MS (m/e), 238 (M⁺), 223, 205, 195,182, 165, 137, 123, 109, 95, 69, 43 (Base);

Odor: Woody fruity

EXAMPLE 35 2-(2,2,3-Trimethylcyclopent-3-en-1-yl)-5-methyl-4-hexenal(mixture of diastereomers)

A 3 liter 3 neck flask fitted with a mechanical agitator, thermometer,Dean-Stark trap, and condenser was charged with 230 g of2-(2,2,3-trimethylcyclopent-3-en-1-yl)acetaldehyde at 86.6% purity (1.31moles), 250 g of 2-methyl-3-buten-2-ol (2.90 moles), 1000 ml of tolueneand 0.4 g of p-TSA. The flask was heated to reflux and 37 ml of awater/alcohol mixture was distilled off after 24 hours. The flask wascooled and the contents were washed with 500 ml of 10% sodium carbonateand 500 ml of brine. The crude product, 354.4 g, was distilled to afford146 g of purified aldehyde (51% yield). BP 82° C./0.15 mmHg; ¹ H-NMR(300 MHz), δ 0.84 (3H, s), 0.96 (3H, s), 1.60 (6H, s), 1.67 (3H, s),2.0-2.5 (6H, m), 5.05 (1H, br s), 5.25 (1H, s), 9.57 (1H, d, J=5.25 Hz);¹³ C-NMR (75 MHz), δ 12.58, 17.94, 20.20, 25.83, 26.32, 27.62, 34.04,47.12, 49.99, 54.74, 120.85, 121.45, 134.16, 149.31, 206.46; IR (Neat),2980, 1730, 1450, 1370 cm⁻¹ ; MS (m/e), 220 (M⁺), 205, 108 (Base);

Odor: Fatty fresh aldehyde green muguet

EXAMPLE 36 2-(2,2,3-Trimethylcyclopent-3-en-1-yl)-5-methyl-4-hexenol(mixture of diastereomers)

Similar to Example 2, 20.3 g of the aldehyde from Example 35 at 80.7%purity (0.074 mole), 1.6 g of sodium borohydride (0.042 mole), 70 ml ofethanol were reacted in the usual way to afford 19.5 g of crude alcoholwhich was distilled to afford 13.0 g of purified alcohol (79% yield). BP80° C./0.08 mmHg; ¹ H-NMR (300 MHz), δ 0.88 (3H, s), 1.07 (3H, s), 1.60(3H, s), 1.65 (3H, s), 1.71 (3H, s), 1.5-1.7 (2H, m), 1.8-2.3 (5H, m),3.65 (2H, m), 5.22 (2H, br s); ¹³ C-NMR (75 MHz), δ 12.66, 17.92, 19.76,26.02, 27.36, 28.47, 34.05, 42.04, 47.09, 49.83, 64.48, 122.00, 123.28,133.30, 149.16; IR (Neat), 3350, 2980, 1450, 1370, 1040 cm⁻¹ ; MS (m/e),222 (M⁺), 207, 191, 135, 121, 112, 95, 41 (Base);

Odor: Weak floral rosey honey

EXAMPLE 372,2-Dimethyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydropyran(mixture of diastereomers)

Similar to Example 3, 128 g of the alcohol from Example 36 at 93.7%purity (0.540 mole), 3.5 g of p-TSA, and 400 ml of heptane were refluxedfor 120 hours. The usual work-up afforded 135.9 g of crudetetrahydropyran which was distilled to afford 92.7 g of purified product(78% yield). BP 85° C./0.25 mmHg; ¹ H-NMR (300 MHz), δ 0.88 (3H, s),1.02 (3H, s), 1.10 (3H, s), 1.19 (3H, s), 1.57 (3H, s), 1.4-2.3 (5H, m),3.2-3.9 (2H, m), 5.20 (1H, s); ¹³ C-NMR (75 MHz), δ 12.51, 19.17, 21.68,25.91, 27.16, 31.08, 33.36, 36.57, 46.73, 48.06, 52.47, 66.60, 70.63,121.30, 148.65; IR (Neat), 2980, 1450, 1370, 1090 cm⁻¹ ; MS (m/e), 222(M⁺), 207, 191, 149, 121, 112, 108, 95, 41 (Base);

Odor: Weak piney

EXAMPLE 38 2,2-Dimethyl-5-(2,2,3-trimethylcyclopent-1-yl)tetrahydropyran(mixture of diastereomers)

The tetrahydropyran from Example 37, 40.5 g at 91.4% purity (0.166mole), was hydrogenated in a Parr shaker with 1.0 g of 5% Pd on carbonin 40 ml of ethanol at 35°-45° C. The resultant product, 40.7 g, wasdistilled to afford 37.3 g of purified product (100% yield). BP 86°C./0.4 mmHg; ¹ H-NMR (300 MHz), δ 0.62 (3H, s), 0.78 (3H, d, J=6.72 Hz),0.90 (3H, s), 0.95-1.05 (2H, m), 1.17 (3H, s), 1.18 (3H, s), 1.2-1.8(9H, m), 3.2-3.9 (2H, m); ¹³ C-NMR, δ 13.68, 14.34, 21.44, 25.87, 26.61,27.14, 29.65, 31.20, 36.70, 38.31, 42.42, 45.85, 52.87, 66.36, 70.52; IR(Neat), 2980, 1470, 1370, 1090 cm⁻¹ ; MS (m/e), 224 (M⁺), 209, 191, 123,109, 95, 69, 43 (Base);

Odor: Weak woody

EXAMPLE 39[rac]-2,2-Dimethyl-5-(2,3,3-trimethylcyclopent-1-en-1-yl)tetrahydropyran

The tetrahydropyran from Example 37, 38.5 g at 90.8% purity, 250 ml ofheptane, and 2.5 g of Amberlyst-15 were refluxed for 4 hours at 95° C.The resultant product, 40 g, was distilled to afford 30 g of purifiedproduct (88% yield). BP 80° C./0.45 mmHg; ¹ H-NMR (300 MHz), δ 0.95 (6H,s), 1.22 (6H, s), 1.52 (3H, s), 1.5-1.72 (6H, m), 2.1 (2H, m), 2.51 (1H,m), 3.4 (2H_(AB), AB Quartet, J_(AB) =11.4 Hz); ¹³ C-NMR (75 MHz), δ9.33, 21.42, 24.52, 26.28, 26.60, 29.49, 31.37, 36.36, 36.50, 38.85,46.64, 64.43, 70.72, 133.17, 140.67; IR (Neat), 2980, 1460, 1370, 1085cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 191, 121 (Base);

Odor: Weak woody

EXAMPLE 40 2,2-Dimethyl-5-(2,3,3-trimethylcyclopent-1-yl)tetrahydropyran(mixture of diastereomers)

The tetrahydropyran from Example 39, 24.6 g at a purity of 77.6% (0.086mole) was hydrogenated using 2.0 g of 5% Pd on carbon in 50 ml ofethanol at a temperature of 60°-80° C. The resulting crude product, 24.9g, was distilled to afford 19 g of purified tetrahydropyran (98% yield).BP 82° C./0.3 mmHg; ¹ H-NMR (300 MHz), δ 0.74 (3H, s), 0.85 (3H, d,J=6.75 Hz), 0.93 (3H, s), 1.18 (3H, s), 1.20 (3H, s), 1.2-1.8 (11H, m),3.35-3.7 (2H, m); ¹³ C-NMR (75 MHz), δ 14.04, 14.94, 22.08, 25.44,26.33, 28.34, 31.08, 36.74, 39.25, 40.23, 40.76, 46.38, 46.94, 66.42,71.07; IR (Neat), 2980, 1470, 1370, 1090 cm⁻¹ ; MS (m/e), 224 (M⁺), 209,191, 151, 135, 123, 110, 95 (Base);

Odor: Weak woody

EXAMPLE 41 2,5-Dimethyl-2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-hexenal(mixture of diastereomers)

In a procedure similar to Example 35,2-(2,2,3-trimethylcyclopent-3-en-1-yl)propanal (from Example 5), 115 gat 94% purity (0.65 mole), 125 g of 2-methyl-3-buten-2-ol (1.45 moles),500 ml of heptane, and 0.55 g of p-TSA were refluxed for 72 hours. Atotal of 15 ml of an H₂ O/alcohol mixture was distilled off. A GC sampleshows 11% starting material and 83.6% product. After the usual work-up189.2 g of crude product were obtained. The product was distilled toafford 118 g of purified aldehyde (78% yield). BP 92° C./0.2 mmHg; ¹H-NMR (300 MHz), δ 0.87 (3H, s), 1.05 (3H, s), 1.07 (3H, s), 1.56 (3H,s), 1.61 (3H, s), 1.69 (3H, s), 2.1-2.45 (5H, m), 5.02 (1H, m), 5.28(1H, s), 9.71 (1H, s); ¹³ C-NMR (75 MHz), δ 12.34, 16.16, 17.95, 22.39,26.00, 28.03, 30.90, 35.82, 48.14, 52.78, 55.38, 118.80, 121.10, 134.68,148.07, 206.87; IR (Neat), 2980, 2710, 1720, 1450, 1380; MS (m/e), 234(M⁺), 219, 205, 126, 108, 69, 41 (Base);

Odor: Floral quinoline

EXAMPLE 42 2,5-Dimethyl-2-(2,2,3-trimethylcyclopent-3-en-1-yl)-4-hexenol(mixture of diastereomers)

A 1 liter 4 neck flask fitted with mechanical agitator, nitrogen inlet,250 ml side arm dropping funnel, thermometer and condenser was chargedwith 8.0 g of lithium aluminum hydride (0.21 mole) and 500 ml of dryether. The flask was cooled to 5° C. and 101.3 g of the aldehyde fromExample 41 at a purity of 97% (0.419 mole) in 125 ml of dry ether wasadded dropwise to the flask. After the addition the contents werestirred for 30 minutes at 5° C., then the reaction was quenched at 5° C.by the addition of 16 ml of H₂ O, then 12.8 ml of 10% sodium hydroxide.The batch was filtered and concentrated in vacuo to afford 100.8 g ofcrude alcohol. The alcohol was distilled from 1 g of sodium carbonate toafford 98.3 g of purified product (99% yield). BP 114° C./0.3 mmHg; ¹H-NMR (300 MHz), δ 1.00 (6H, s), 1.13 (3H, s), 1.56 (3H, s), 1.56 (3H,s), 1.65 (3H, s), 1.67 (1H, m), 1.72 (3H, s), 2.08 (5H, m), 3.60(2H_(AB), AB quartet, J_(AB) =11.0 Hz), 5.28 (2H, br s); ¹³ C-NMR (75MHz), δ 12.35, 17.93, 19.45, 22.31, 26.19, 28.32, 30.88, 36.38, 41.96,48.16, 54.05, 68.87, 120.75, 121.41, 133.52, 148.37; IR (Neat), 3380,2980, 1450, 1370, 1040 cm⁻¹ ; MS (m/e), 236 (M⁺), 221, 205, 149, 121,109 (Base);

Odor: Weak floral

EXAMPLE 432,2,5-Trimethyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)tetrahydropyran(mixture of diastereomers)

Similar to Example 8, the alcohol from Example 42, 60.3 g at 96.7%purity (0.247 mole), 450 ml of heptane, and 1.5 g of p-TSA were refluxedfor 36 hours. The crude product, 64.2 g, was distilled to afford 49 g ofpurified tetrahydropyran (84% yield). BP 90° C./0.3 mmHg; ¹ -NMR (300MHz), δ 0.88 (3H, s), 0.98 (3H, s), 1.12 (3H, s), 1.18 (3H, s), 1.21(3H, s), 1.55 (3H, s), 1.4-2.2 (7H, m), 3.2-3.7 (2H, m), 5.3 (1H, m); ¹³C-NMR (75 MHz), δ 12.28, 19.17, 22.22, 23.37, 27.53, 30.31, 32.33,35.79, 38.74, 45.36, 50.66, 56.84, 70.14, 71.54, 121.26, 148.40; IR(Neat), 2980, 1455, 1370, 1075 cm⁻¹ ; MS (m/e), 236 (M⁺), 221, 205, 193,149, 135, 126, 108 (Base);

Odor: Fresh spicy ginger milky green nootkatone

EXAMPLE 44 2-(3,3-Dimethylbicyclo[2.2.1]hept-2-yl)-4-methyl-4-pentenal(mixture of diastereomers)

In a similar procedure as in Example 1, 247 g of3,3-dimethylbicyclo[2.2.1]hept-2-yl acetaldehyde at 93.3% purity (1.39moles), 220 g of methallyl alcohol (3.0 moles), 800 ml of heptane and1.0 g of p-TSA were refluxed for 16 hours while collecting 29.5 ml ofwater/alcohol mixture. The usual work-up afforded 414.7 g of crudeacetal. BP 118° C./0.3 mmHg; ¹ H-NMR (300 MHz), δ 0.81 (3H, s), 0.94(3H, s), 0.98-1.7 (11H, m), 1.76 (6H, s), 3.96 (4H, m), 4.55 (1H, m),4.88 (2H, s), 4.99 (2H, s); ¹³ C-NMR (75 MHz), δ 19.78, 21.86, 24.75,27.82, 30.23, 32.29, 35.81, 37.12, 41.43, 45.89, 49.02, 68.81, 102.21,111.86, 142.29; IR (Neat), 2980, 1660, 1460, 1370, 1130, 1030, 900 cm⁻¹; MS (m/e), 221 (M⁺ -71), 155, 109, 55 (Base);

Odor: Weak

The crude acetal, 364.4 g, was heated with 2.0 g of citric acid at about120 mmHg to a maximum temperature of 168° C. Methallyl alcohol, 78.7 g,was collected. When the distillation ends the reaction was heated for 2hours at 160° C. The batch was cooled and washed with water, 10% sodiumcarbonate and brine. The crude aldehyde, 285 g, was distilled to afford152 g of purified product (56% yield). BP 88° C./0.3 mmHg; ¹ H-NMR (300MHz), δ 0.86 (3H, s), 0.99 (3H, s), 1.25 (2H, m), 1.5-1.8 (6H, m), 1.73(3H, s), 2.1-2.4 (4H, m), 4.67 (1H, s), 4.75 (1H, s), 9.54 (1H, d,J=4.32 Hz); ¹³ C-NMR (75 MHz), δ 20.49, 22.46, 24.66, 26.19, 27.91,32.24, 36.30, 38.49, 40.22, 48.18, 50.06, 54.55, 112.81, 142.25, 205.39;IR (Neat), 2980, 2700, 1730, 900 cm⁻¹ ; MS (m/e), 220 (M⁺), 205, 191,177, 164, 151, 136, 121, 109, 41 (Base);

Odor: Fruity

EXAMPLE 45 2-(3,3-Dimethylbicyclo[2.2.1]hept-2-yl)-4-methyl-4-pentenol(mixture of diastereomers)

Similar to Example 7, 82.7 g of the aldehyde from Example 44 at a purityof 86% (0.32 mole), 44.2 g of aluminum isopropoxide (0.22 mole) and 155g of isopropanol were reacted to afford 81.3 g of crude alcohol. Theproduct was distilled from 1 g of soda ash to afford 61 g (85% yield) ofpurified alcohol. BP 97° C./0.2 mmHg; ¹ H-NMR (300 MHz), δ 0.97 (3H, s),1.01 (3H, s), 1.1-1.3 (4H, m), 1.6-1.8 (5H, m), 1.81 (3H, s), 1.9-2.3(4H, m), 3.4-3.7 (2H, m), 4.78 (1H, s), 4.84 (1H, s); ¹³ C-NMR (75 MHz),δ 20.16, 21.82, 22.51, 23.82, 25.16, 28.88, 31.18, 36.24, 39.72, 40.62,50.45, 54.60, 65.81, 111.83, 146.78; IR (Neat), 3390, 2960, 1650, 1460,1370, 1050, 1040 cm⁻¹ ; MS (m/e), 207 (M⁺ -15), 191, 166, 48, 135, 122,107, 93, 81, 67, 55, 41 (Base);

Odor: Weak

EXAMPLE 462,2-Dimethyl-4-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, the alcohol from Example 45, 40.4 g, at a purityof 92.3% (0.168 mole), was refluxed for about 1 hour with 1.0 g ofAmberlyst-15 in 150 ml of hexane. After the usual work-up 39.4 g ofcrude product was obtained. This material was distilled to afford 35.4 gof purified product (95% yield). BP 86° C./0.4 mmHg; ¹ H-NMR (300 MHz),δ 0.86 (3H, s), 0.92 (3H, s), 1.1-1.4 (5H, m), 1.19 (3H, s), 1.27 (3H,s), 1.6-2.5 (7H, m), 3.4 (1H, m), 4.02 (1H, m); ¹³ C-NMR (75 MHz), δ21.17, 22.57, 25.17, 28.31, 29.20, 30.78, 33.37, 38.93, 43.35, 46.04,50.29, 56.30, 60.83, 72.74, 80.23; IR (Neat), 2980, 1460, 1370, 1110cm⁻¹ ; MS (m/e), 222 (M⁺), 207 (Base), 149, 109;

Odor: Woody amber

EXAMPLE 47 3-(3,3-Dimethylbicyclo[2.2.1]hept-2-yl)-5-methyl-5-hexen-2-ol(mixture of diastereomers)

Similar to Example 11, 35.0 g of the aldehyde from Example 44 at apurity of 90.5% (0.143 mole), 66 ml of 3.0M methylmagnesium bromide in250 ml of dry ether afforded 34.4 g of crude alcohol. This alcohol wasdistilled from 1 g of soda ash to afford 21 g of purified product (62%yield); BP 97° C./0.1 mmHg; ¹ H-NMR (300 MHz), δ 1.03 (3H, s), 1.05 (3H,s), 1.08-1.17 (4H, m), 1.23 (3H, d, J=6.84 Hz), 1.60-1.87 (7H, m), 1.79(3H, s), 2.0-2.3 (2H, m), 3.86 (1H, q, J=6.66 Hz), 4.76 (1H, s), 4.80(1H, s); ¹³ C-NMR (75 MHz) consistent with assigned structures; IR(Neat) 3400, 2970, 1650, 1470, 1370, 1130, 1080, 1050, 890 cm⁻¹ ; MS(m/e), 221 (M⁺ -15), 203, 192, 177, 163, 149, 108 (Base), 43;

Odor: Weak

EXAMPLE 482,2,5-Trimethyl-4-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 19.1 g of the alcohol from Example 47 at 100%purity (0.08 mole), 80 ml of heptane, and 1.0 g of Amberlyst-15 wererefluxed for 2 hours. After the usual work-up 20.3 g of crudetetrahydrofuran was distilled to afford 16.8 g of purified product (88%yield). BP 65° C./0.04 mmHg; ¹ H-NMR (300 MHz), spectra consistent withassigned structures; ¹³ C-NMR (75 MHz), spectra consistent with assignedstructures; IR (Neat), 2980, 1465, 1370, 1090 cm⁻¹ ; MS (m/e), 221 (M⁺-15), 203, 192, 177, 163, 149, 136, 123, 108 (Base), 93, 81, 67, 43;

Odor: Amber dry tobacco

EXAMPLE 49 2-(3,3-Dimethylbicyclo[2.2.1]hept-2-yl)propenal (mixture ofdiastereomers)

A 4 neck 3 liter bottom drain flask equipped with condenser, nitrogeninlet, mechanical agitator, thermometer and 60 ml side arm droppingfunnel was charged with 1044 g of 3,3-dimethylbicyclo[2.2.1]hept-2-ylacetaldehyde (6.02 moles), 533 g of 37% formaldehyde (6.57 moles) and2.2 g of BHT. The contents were brought to reflux (98° C.) and 25.9 g ofdiethylamine (0.35 mole) were added over 15 minutes. The batch wasrefluxed for 18.5 hours. The flask was brought to 60° C. and 65 g of 37%formaldehyde (0.80 mole) and 12.7 g of diethylamine (0.17 mole) wereadded and reflux was continued for 5 hours. The flask was cooled and theoil layer was separated from the aqueous layer. The oil was washed with36 g of acetic acid (0.6 mole) for 10 minutes, then 300 ml of brine wasadded and stirring continued for 5 minutes. Then 300 ml of heptane wasadded and the batch was stirred for 5 minutes. The top organic layer waswashed with 400 ml of a 1:1 mixture of 10% sodium carbonate and brine.The organic layer was washed with 500 ml of brine. All the aqueouswashings were back extracted with 300 ml of heptane. The organicwashings were dried, filtered and concentrated in vacuo to afford 1148 gof crude product. The aldehyde was distilled to afford 810 g of purifiedproduct (72% yield). BP 95° C./2.2 mmHg; ¹ H-NMR (300 MHz), δ 0.61 (3H,s), 1.17 (3H, s), 1.2-1.75 (7H, m), 2.20 (2H, m), 5.98 (1H, s), 6.30(1H, s), 9.51 (1H, s); ¹³ C-NMR (75 MHz), δ 21.47, 24.23, 26.22, 29.94,36.95, 41.53, 42.26, 49.35, 51.25, 132.54, 153.05, 195.62; IR (Neat),2980, 2810, 2760, 2700, 1690, 1470, 1370 cm⁻¹ ; MS (m/e), 178 (M⁺), 163,145, 135, 107, 79, 67, 41 (Base);

Odor: Borneol camphor

EXAMPLE 50 2-(3,3-Dimethylbicyclo[2.2.1]hept-2-yl)propanal (mixture ofdiastereomers)

The crude aldehyde from Example 49, 271.5 g at 85% purity (1.29 moles)was hydrogenated on a Parr shaker using 5.0 g of 5% Pd on carbon and 5.0g of sodium carbonate. In this way 254.6 g of crude propanal wereobtained. The batch was distilled to afford 176.7 g of purified product(66% yield); BP 50° C./0.08 mmHg; ¹ H-NMR (300 MHz), δ 1.03 (6H, s),1.09 (3H, d, J=6.42 Hz), 1.2-1.7 (9H, m), 2.36 (1H, m), 9.50 (1H, d,J=4.53 Hz); ¹³ C-NMR (75 MHz), δ 13.98, 15.45, 21.95, 23.90, 26.12,28.68, 30.61, 36.15, 41.62, 49.88, 56.07, 204.80; IR (Neat), 2980, 2700,1730, 1470, 1370 cm⁻¹ ; MS (m/e), 180 (M⁺), 165, 151, 122, 109, 95, 41(Base);

Odor: Camphor medicinal

EXAMPLE 512,4-Dimethyl-2-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)-4-pentenal (mixtureof diastereomers)

Similar to Example 6, 80.0 g of the aldehyde in Example 50, at a purityof 93.6% (0.46 mole) in 40 ml of DMF, 60 g of potassium t-butoxide (0.51mole) in 250 ml of DMF, and 60 g of methallyl chloride (0.63 mole) in 40ml of DMF, were reacted in the usual way to afford 97.9 g of crudeC-alkylate and O-alkylate (approximately 1:1). The mixture was heated at165°-175° C. for 2 hours to afford 93.9 g of crude product. This productwas distilled to afford 85.9 g of purified aldehyde (83% yield). BP 90°C./0.15 mmHg; ¹ H-NMR (300 MHz), δ 1.05 (6H, s), 1.11 (3H, s), 1.13-1.3(3H, m), 1.5-2.7 (5H, m), 1.61 (3H, s), 2.19-2.55 (3H, m), 4.66 (1H, s),4.84 (1H, s), 9.74 (1H, s); ¹³ C-NMR (75 MHz), δ 15.45, 23.81, 26.41,29.46, 31.93, 34.21, 37.30, 40.31, 43.84, 47.74, 50.06, 53.45, 59.85,115.85, 141.38, 207.52; IR (Neat), 2980, 2700, 1725, 1650, 1470, 1370,895 cm⁻¹ ; MS (m/e), 219 (M⁺ -15), 191, 178, 149, 135, 123, 109, 95(Base);

Odor: Woody amber

EXAMPLE 52 2,4-Dimethyl-2-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)-4-pentenol (mixture of diastereomers)

Similar to Example 2, 63.4 g of the aldehyde from Example 51 at a purityof 98% (0.265 mole), 6.0 g of sodium borohydride (0.158 mole), and 200ml of ethanol were reacted in the usual way. The crude alcohol, 62.6 g,was distilled to afford 41 g of product (65% yield). BP 92° C./0.1 mmHg;¹ H-NMR (300 MHz), δ 1.03 (3H, s), 1.10 (3H, s), 1.17 (3H, s), 1.1-1.3(2H, m), 1.3-1.7 (7H, m), 1.83 (3H, s), 2.1-2.4 (3H, m), 3.4-3.65 (2H,m), 4.75 (1H, s), 4.87 (1H, s); ¹³ C-NMR (75 MHz), δ 20.08, 23.37,25.45, 26.80, 26.91, 29.61, 32.73, 37.46, 40.09, 43.21, 44.43, 51.09,59.37, 69.19, 114.71, 144.70; IR (Neat), 3400, 2980, 1640, 1470, 1370,1040, 890 cm⁻¹ ; MS (m/e), 221 (M⁺ -15), 205, 181, 163, 149, 135, 123,107, 93, 81, 67, 55, 41 (Base);

Odor: Weak

EXAMPLE 532,2,4-Trimethyl-4-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 33.4 g of the alcohol from Example 52 at a purityof 96.8% (0.136 mole), 0.5 g of Amberlyst-15 and 150 ml of heptane wererefluxed for 12 hours. After the usual work-up, 35.6 g of crudetetrahydrofuran was distilled to afford 31.8 g of purified product (98%yield). BP 75° C./0.08 mmHg; ¹ H-NMR (300 MHz), δ 1.01 (3H, s), 1.05(3H, s), 1.21 (3H, s), 1.24 (3H, s), 1.31 (3H, s), 1.1-1.3 (2H, m),1.35-2.05 (9H, m), 3.58 (2H, m); ¹³ C-NMR (75 MHz), δ 23.67, 26.36,26.63, 28.04, 29.24, 29.41, 32.22, 37.19, 41.65, 43.64, 48.23, 50.08,58.60, 63.23, 77.49, 80.10; IR (Neat), 2980, 1460, 1370, 1060 cm⁻¹ ; MS(m/e), 236 (M⁺), 221, 205, 193, 163, 149, 135, 125, 109, 43 (Base);

Odor: Woody amber

EXAMPLE 54 2-Methyl-2-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)-4-pentenal(mixture of diastereomers)

Similar to Example 6, 330.3 g of the aldehyde from Example 50, at apurity of 92.3% (1.69 moles) in 160 ml of DMF, 223.9 g of potassiumt-butoxide (1.89 moles) in 1000 ml of DMF, and 165.8 g of allyl chloride(2.12 moles) in 160 ml of DMF were reacted in the usual manner to afford401.9 g of crude C- and O-alkylate. This material was heated undernitrogen at 165° C. for 2.5 hours to afford the crude C-alkylate whichwas distilled to afford 64.2 g of purified aldehyde (81% yield). BP 95°C./0.15 mmHg; ¹ H-NMR (300 MHz), δ 0.93 (3H, s), 1.06 (3H, s), 1.11 (3H,s), 1.1-1.7 (5H, m), 2.2-2.5 (3H, m), 5.05 (2H, m), 5.6 (1H, m), 9.64(1H, s); ¹³ C-NMR (75 MHz), δ 16.18, 23.15, 26.26, 29.33, 31.97, 33.95,37.95, 39.94, 43.08, 49.93, 52.97, 59.35, 118.00, 133.29, 206.70; IR(Neat), 2980, 2700, 1725, 1640, 1470, 1370, 920 cm⁻¹ ; MS (m/e), 220(M⁺), 205, 179, 161, 135, 121, 109, 95, 81, 41 (Base);

Odor: Woody amber

EXAMPLE 55 2-Methyl-2-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)-4-pentenol(mixture of diastereomers)

Similar to Example 2, 58.8 g of the aldehyde from Example 54, at apurity of 97.5% (0.260 mole), 4.0 g of sodium borohydride (0.105 mole),and 175 ml of ethanol were reacted in the usual way to afford 59.5 g ofcrude alcohol. The alcohol was distilled to afford 49.7 g of purifiedproduct (86% yield). BP 97° C./0.15 mmHg; ¹ H-NMR (300 MHz), δ 0.96 (3H,s), 1.12 (3H, s), 1.17 (3H, s), 1.2-1.8 (5H, m), 2.1-2.24 (4H, m), 3.52(2H, br s), 5.06 (2H, m), 5.9 (1H, m); ¹³ C-NMR (300 MHz), δ 19.39,23.37, 26.96, 29.44, 32.71, 37.43, 39.79, 41.49, 42.78, 44.31, 51.05,58.20, 68.71, 117.12, 136.10; IR (Neat), 3400, 2980, 1640, 1470, 1370,1040, 910 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 191, 181, 163, 135, 123, 107,81, 67 (Base);

Odor: Weak woody

EXAMPLE 562,4-Dimethyl-4-(3,3-dimethylbicyclo[2.2.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 31.4 g of the alcohol from Example 55 at a purityof 100% (0.141 mole), 1.0 g of Amberlyst-15, and 150 ml of heptane wererefluxed for about 16 hours. After the usual work-up, the crudetetrahydrofuran, 34.1 g, was distilled to afford 29.4 g of purifiedproduct (93.6% yield). BP 70° C./0.04 mmHg; ¹ H-NMR (300 MHz), δ 1.00(3H, s), 1.06 (3H, s), 1.13 (3H, s), 1.22 (3H, d, J=6.03 Hz), 1.0-1.4(4H, m), 1.5-2.3 (7H, m), 3.4-4.1 (3H, m); ¹³ C-NMR (75 MHz), δ 20.92,22.52, 23.68, 26.35, 29.72, 31.97, 34.74, 37.23, 41.69, 43.37, 49.96,50.10, 63.28, 74.00, 79.07; IR (Neat), 2980, 1470, 1370, 1080, 1055,1050 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 189, 179, 161, 135, 109 (Base);

Odor: Woody amber

EXAMPLE 57 2-(6,6-Dimethylbicyclo[3.1.1]hept-2-yl)propenal (mixture ofdiastereomers)

In a similar manner to Example 49, 342 g of6,6-dimethylbicyclo[3.1.1]hept-2-yl acetaldehyde at a purity of 97%(1.99 moles), 178 g of 37% formaldehyde (2.2 moles), 7.3 g ofdiethylamine (0.1 mole), and 0.8 g of BHT were refluxed for 1.5 hours.After the usual work-up, 370 g of crude propenal was distilled to afford317 g of purified product (89% yield). BP 75° C./0.5 mmHg; ¹ H-NMR (300MHz), δ 0.92 (3H, s), 1.23 (3H, s), 1.47-2.40 (8H, m), 3.1 (1H, t,J=8.91 Hz), 5.91 (1H, s), 6.20 (1H, s), 9.50 (1H, s); ¹³ C-NMR (75 MHz),δ 20.06, 20.92, 23.88, 26.76, 28.03, 32.82, 40.08, 41.32, 44.34, 131.53,155.46, 194.97; IR (Neat), 2960, 2700, 1690, 940 cm⁻¹ ; MS (m/e), 177(M⁺ -1), 163, 145, 135, 121, 107, 91, 79, 41 (Base);

Odor: Piney camphoraceous

EXAMPLE 58 2-(6,6-Dimethylbicyclo[3.1.1]hept-2-yl)propanal (mixture ofdiastereomers)

281 g of the propenal in Example 57 (1.53 moles) were hydrogenated on aParr shaker with 2.7 g of 5% Pd on carbon. The resulting propanal, 282g, was distilled to afford 242 g of purified product (87% yield). BP 64°C./0.4 mmHg; ¹ H-NMR (300 MHz), δ 0.95 (3H, s), 1.02 (3H, s), 1.20 (3H,d, J=7.62 Hz), 1.30-2.50 (10H, m), 9.62 (1H, d, J=2.55 Hz); ¹³ C-NMR (75MHz), δ 11.29, 20.16, 23.47, 24.39, 26.84, 27.95, 36.31, 40.33, 42.72,44.16, 51.68, 205.56; IR (Neat) 2960, 2700, 1735, 1470, 1370; MS (m/e),165 (M⁺ -15), 149, 137, 122, 107, 95, 79, 69, 55, 41 (Base);

Odor: Camphoraceous piney fruity

EXAMPLE 59 2-(6,6-Dimethylbicyclo[3.1.1]hept-2-yl)-4-m ethyl-4-pentenal(mixture of diastereomers)

In a manner similar to Example 6, 90 g of6,6-dimethylbicyclo[3.1.1]hept-2-yl acetaldehyde (0.529 mole) in 40 mlof DMF, 108 g of potassium t-butoxide (0.91 mole) in 400 ml of DMF, and93 g of methallyl chloride (1.02 moles) in 40 ml of DMF were reacted inthe usual manner. After work-up the crude mixture of C- and O-alkylates,112 g, was heated at 165°-175° C. for 4 hours. The crude product wasdwastilled to afford 34.5 g of purified product (30% yield). BP 90°C./0.1 mmHg; ¹ H-NMR (300 MHz), δ 1.06 (3H, s), 1.16 s), 1.69 (3H, s),1.3-2.6 (12H, m), 4.67 (1H, s), 4.74 (1H, s), 9.36 (1H, m); ¹³ C-NMR (75MHz), spectra consistent with assigned structures; IR (Neat) 2960, 2700,1730, 1650, 1470, 1370, 890 cm⁻¹ ; MS (m/e), 220 (M⁺), 205, 189, 177,163, 149, 135, 121, 107, 93, 79, 69, 41 (Base);

Odor: Fruity raspberry sweet

EXAMPLE 60 2-(6,6-Dimethylbicyclo[3.1.1]-hept-2-yl)-4-methyl-4-pentenol(mixture of diastereomers)

In a reduction similar to Example 42, the aldehyde from Example 59, 21.5g (0.091 mole), was added dropwise to 1.78 g of lithium aluminum hydride(0.046 mole) in 100 ml of dry ether at 0° C. After quenching with 3.6 mlof water and 2.8 ml of 10% sodium hydroxide, 21.4 g of crude alcoholwere obtained (100% yield). BP 120° C./0.1 mmHg; ¹ H-NMR (300 MHz), δ1.02 (3H, s), 1.21 (3H, s), 1.73 (3H, s), 1.5-2.3 (12H, m), 3.02 (2H,m), 4.78 (2H, m); ¹³ C-NMR (75 MHz), spectra consistent with assignedstructures; IR (Neat), 3350, 2940, 1650, 1470, 1370, 890 cm⁻¹ ; MS(m/e), 222 (M⁺), 207, 191, 179, 161, 149, 135, 123, 107, 93, 81, 69(Base);

Odor: Weak

EXAMPLE 612,2-Dimethyl-4-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

In a procedure similar to Example 4, 20 g of the alcohol from Example 60at a purity of 85% (0.076 mole), 1.25 g of Amberlyst-15, and 70 ml ofheptane were refluxed for 24 hours. After the usual work-up the crudetetrahydrofuran, 19.6 g, was distilled to afford 15 g of purifiedproduct (88% yield). BP 55° C./0.05 mmHg; ¹ H-NMR (300 MHz), δ 1.05 (3H,s), 1.18 (6H, s), 1.26 (3H, s), 1.5-2.5 (12H, m), 3.36 (1H, m), 3.93(1H, m); ¹³ -NMR (75 MHz), δ 20.06, 21.47, 23.34, 26.41, 28.12, 28.87,33.46, 39.70, 40.65, 41.43, 44.83, 45.04, 46.30, 71.94, 80.64; IR(Neat), 2960, 1470, 1370, 1050 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 191, 165,149, 137, 123, 107, 69, 43 (Base);

Odor: Woody fruity

EXAMPLE 62 2-(6,6-Dimethylbicyclo[3.1.1]hept-2-yl)-4-pentenal (mixtureof diastereomers)

In a procedure similar to Example 6, 100 g of6,6-dimethylbicyclo[3.1.1]hept-2-yl acetaldehyde at a purity of 98.3%(0.59 mole) in 50 ml of DMF, 82 g of potassium t-butoxide (0.69 mole) in300 ml of DMF, and 55 g of allyl chloride in 50 ml of DMF (0.78 mole)were reacted in the usual way to afford 110.5 g of crude productcomposed of 36% starting material, 31% O-alkylate and 21% C-alkylate.The product was heated at 165°-185° C. for 6 hours. The crude aldehyde,105.6 g, was distilled to afford 21.4 g of purified product (17% yield).A major impurity in the crude was the dialkylation product. BP product114° C./1.2 mmHg; ¹ H-NMR (300 MHz), δ 1.05 (3H, s), 1.21 (3H, s),1.3-2.6 (12H, m), 5.01 (2H, m), 5.7 (1H, m), 9.47 (1H, m); ¹³ C-NMR (75MHz), spectra consistent with assigned structures; IR (Neat), 2970,2700, 1730, 1640, 1450, 1370, 910 cm⁻¹ ; MS (m/e), 205 (M⁺ -1), 191,175, 163, 122, 107, 93, 41 (Base);

Odor: Berry butyric

EXAMPLE 63

2-(6,6-Dimethylbicyclo[3.1.1]hept-2-yl)-4-pentenol (mixture ofdiastereomers)

In a reaction similar to Example 42, 18.9 g of the aldehyde from Example62 at a purity of 81% (0.074 mole), 1.70 g of lithium aluminum hydride(0.044 mole) in 40 ml of dry ether, were reacted to produce 18.7 g ofcrude alcohol. A sample was flash distilled. BP 110°120° C./0.1 mmHg; ¹H-NMR (300 MHz), spectra consistent with assigned structures; ¹³ C-NMR(75 MHz), spectra consistent with assigned structures; IR (Neat), 3320,2960, 1640, 1370, 1420, 1020, 910 cm⁻¹ ; MS (m/e), 193 (M⁺ -15), 177,163, 147, 123, 107, 93, 81, 67, 41 (Base).

EXAMPLE 642-Methyl-4-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)tetrahydrofuran (mixtureof diastereomers)

Similar to Example 4, 17.1 g of the alcohol from Example 63 at a purityof 80% (0.065 mole), 2.0 g of Amberlyst-15, and 70 ml of heptane wererefluxed for 3 hours. The resulting 16.7 g of crude tetrahydrofuran weredistilled to afford 13.1 g of purified product (95% yield). BP 72°C./0.05 mmHg; ¹ -NMR (300 MHz) spectra consistent with assignedstructures; ¹³ C-NMR (75 MHz) spectra consistent with assignedstructures; IR (Neat), 2960, 1470, 1370, 1100, 1040 cm⁻¹ ; MS (m/e), 193(M⁺ -15), 175, 161, 151, 123, 107, 95, 83, 41 (Base);

Odor: Woody amber weak fruity

EXAMPLE 652,4-Dimethyl-2-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)-4-pentenal (mixtureof diastereomers)

In a similar manner to Example 6, 100 g of the aldehyde from Example 58at a purity of 85% (0.47 mole) in 75 ml of DMF, 82 g of potassiumt-butoxide (0.69 mole) in 500 ml of DMF, and 78 g of methallyl chloride(0.86 mole) in 50 ml of DMF were reacted in the usual way. In this way116.2 g of crude O- and C-alkylates (58.1:33.8) were obtained. The crudeproduct was heated at 165°-170° C. for 2 hours. The crude aldehyde wasdistilled to afford 94.1 g of purified product (85% yield). BP 85°C./0.05 mmHg; ¹ H-NMR (300 MHz), δ 0.95 (3H, s), 0.96 (3H, s), 1.18 (3H,s), 1.2-1.4 (2H, m), 1.59 (3H, s), 1.7-2.5 (9H, m), 4.64 (1H, s), 4.80(1H, s), 9.57 (1H, s); ¹³ C-NMR (75 MHz), spectra consistent withassigned structures; IR (Neat), 2960, 2700, 1725, 1645, 1470, 1370, 895cm⁻¹ ; MS (m/e), 234 (M⁺), 219, 203, 191, 177, 163, 151, 135, 123, 109,97, 81, 41 (Base);

Odor: Weak

EXAMPLE 66 2-Methyl-2-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)-4-pentenal(mixture of diastereomers)

In a similar manner to Example 6, 100 g of the aldehyde from Example 58at a purity of 85% (0.47 mole) in 75 ml of DMF, 90 g of potassiumt-butoxide (0.76 mole) in 500 ml of DMF, and 61.5 g of allyl chloride(0.80 mole) in 50 ml of DMF were reacted in the usual way. In thismanner 111.4 g of crude O- and C-alkylates (25:55) were obtained. Thecrude product was heated at 165°-170° C. for 1 hour affording 108 g ofcrude aldehyde. This material was distilled to afford 85.5 g of purifiedproduct (84% yield). BP 79° C./0.15 mmHg; ¹ H-NMR (300 MHz), δ 0.94 (3H,s), 0.99 (3H, s), 1.19 (3H, s), 1.3-2.5 (11H, m), 5.02 (2H, m), 5.62(1H, m), 9.48 (1H, s); ¹³ C-NMR (75 MHz), spectra consistent withassigned structures; IR (Neat), 2960, 2710, 1725, 1640, 1470, 1370, 920cm⁻¹ ; MS (m/e), 220 (M⁺), 205, 189, 179, 123, 107, 95, 81, 69, 41(Base);

Odor: Woody

EXAMPLE 672,4-Dimethyl-2-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)-4-pentenol (mixtureof diastereomers)

Similar to Example 7, 60 g of the aldehyde from Example 65 at a purityof 97.5% (0.25 mole), 125 ml of isopropanol and 30 g of aluminumisopropoxide were refluxed for 1 hour. The usual work up afforded 59.9 gof crude alcohol. The crude alcohol was distilled to afford 52.1 g ofpurified product (88% yield). BP 103° C./0.09 mmHg; ¹ H-NMR (300 MHz), δ0.82 (3H, s), 0.83 (3H, s), 1.22 (3H, s), 1.79 (3H, s), 1.35-1.8 (6H,m), 1.9-2.2 (6H, m), 3.43 (2H, m), 4.72 (1H, s), 4.87 (1H, s); ¹³ C-NMR(75 MHz), spectra consistent with assigned structures; IR (Neat), 3400,2960, 1640, 1470, 1370, 1030, 890 cm⁻¹ ; MS (m/e), 236 (M⁺), 221, 205,149, 135, 123, 107, 95, 81, 69, 41 (Base);

Odor: Weak

EXAMPLE 68 2-Methyl-2-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)-4-pentenol(mixture of diastereomers)

Similar to Example 7, 60 g of the aldehyde from Example 66 at a purityof 96% (0.26 mole), 125 ml of isopropanol and 32 g of aluminumisopropoxide (0.148 mole) were refluxed for 1 hour. The usual work-upafforded 59.9 g of crude alcohol. The crude alcohol was distilled toafford 52.0 g of purified product (89% yield). BP 92° C./0.05 mmHg; ¹H-NMR (300 MHz), δ 0.78 (3H, s), 0.81 (3H, s), 1.21 (3H, s), 1.38-2.50(12H, m), 3.41 (2H, m), 5.02 (2H, m), 5.87 (1H, m); ¹³ C-NMR (75 MHz), δ16.27, 18.12, 20.14, 24.39, 25.27, 27.05, 29.27, 37.98, 39.65, 40.81,43.37, 47.12, 67.62, 117.04, 135.88; IR (Neat), 3380, 2970, 1640, 1470,1370, 1040, 910 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 191, 161, 135, 123, 107,93, 81, 67, 41 (Base);

Odor: Weak

EXAMPLE 692,2,4-Trimethyl-4-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 45.1 g of the alcohol from Example 67 at a purityof 98.5% (0.188 mole), 1.0 g of Amberlyst-15 and 150 ml of heptane wererefluxed for 24 hours. After the usual work-up 47.7 g of crudetetrahydrofuran were obtained. The crude was distilled to obtain 41 g ofpurified product (92% yield). BP 77° C./0.09 mmHg; ¹ H-NMR (300 MHz), δ0.81 (3H, s), 1.02 (3H, s), 1.20 (6H, s), 1.29 (3H, s), 1.41-2.1 (11H,m), 3.48 (2H, m); ¹³ C-NMR (75 MHz), spectra consistent with assignedstructures; IR (Neat), 2980, 1470, 1370, 1050 cm⁻¹ ; MS (m/e), 236 (M⁺),221, 163, 135, 123, 112, 107, 43 (Base);

Odor: Woody sandalwood

EXAMPLE 702,4-Dimethyl-4-(6,6-dimethylbicyclo[3.1.1]hept-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 45.5 g of the alcohol from Example 68 at a purityof 98.2% (0.20 mole), 1.25 g of Amberlyst-15, and 150 ml of heptane wererefluxed for 24 hours. After the usual work-up, 45.9 g of crudetetrahydrofuran were obtained. The crude was distilled to obtain 38.5 gof purified product (86% yield). BP 79° C./0.2 mmHg; ¹ H-NMR (300 MHz),spectra consistent with assigned structures; ¹³ C-NMR (75 MHz), spectraconsistent with assigned structures; IR (Neat), 2970, 1470, 1370, 1080,1040 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 164, 149, 135, 123, 107, 98, 81,69, 43 (Base);

Odor: Woody powdery amber

EXAMPLE 71 [rac]-2-Methylene-3,5,5-trimethylhexanal

In a similar manner to Example 49, 300 g of 3,5,5-trimethylhexanal at apurity of 95.7% (2.02 moles), 178.4 g of 37% formaldehyde (2.20 moles),7.3 g of diethylamine (0.1 mole), and 0.8 g of BHT were refluxed for 1.5hours. After the usual work-up 323.4 g of crude propenal were distilledto afford 267.3 g of purified product (84% yield). BP 45° C./3 mmHg; ¹H-NMR (300 MHz), δ 0.86 (9H, s), 1.06 (3H, d, J=6.9 Hz), 1.29 (1H, dd,J=14.0, 5.07 Hz), 1.58 (1H, dd, J=14.0, 6.9 Hz), 2.85 (1H, m), 5.96 (1H,s), 6.28 (1H, s), 9.52 (1H, s); ¹³ C-NMR (75 MHz), δ 23.34, 27.89,30.02, 31.32, 49.85, 133.09, 157.60, 194.42; IR (Neat), 2980, 2700,1695, 940 cm⁻¹ ; MS (m/e), 139 (M⁺ -15), 121, 97, 83, 69, 57 (Base);

Odor: Minty camphor

EXAMPLE 72 2,3,5,5-Tetramethylhexanal (mixture of diastereomers)

235 g of the propenal from Example 71 (1.48 moles) were hydrogenated ona Parr shaker with 2.5 g of 5% Pd on carbon. The resulting propanal,231.8 g, was distilled to afford 221.7 g of purified product (96%yield). BP 59° C./5 mmHg; ¹ H-NMR (300 MHz), spectra consistent withassigned structures; ¹³ C-NMR (75 MHz), spectra consistent with assignedstructures; IR (Neat), 2980, 2700, 1730, 1480, 1370; MS (m/e), 141 (M⁺-15), 123, 98, 83, 57 (Base);

Odor: Fresh citrus chlorine

EXAMPLE 73 2,4-Dimethyl-2-(4,4-dimethylpent-2-yl)-4-pentenal (mixture ofdiastereomers)

In a similar manner to Example 6, 100 g of the aldehyde from Example 72at a purity of 96.1% (0.616 mole) in 50 ml of DMF, 90 g of potassiumt-butoxide (0.76 mole) in 500 ml of DMF, and 78 g of methallyl chloride(0.86 mole) in 50 ml of DMF were reacted in the usual way. In thismanner 122.1 g of crude O- and C-alkylates (85.2:5.2) were obtained. Thecrude product was heated at 155°-170° C. for 4.5 hours affording 116.6 gof crude aldehyde. This material was distilled to afford 87 g ofpurified product (67% yield). BP 50° C./0.03 mmHg; ¹ H-NMR (300 MHz), δ0.88 (9H, s), 0.91 (3H, s), 0.92 (1H, m), 0.98 (3H, d, J=6.6 Hz), 1.16(1H, m), 1.64 (3H, s), 1.78 (1H, m), 2.18 (1H_(A), A part of AB quartet,J_(AB) =14.0 Hz), 2.43 (1H_(B), B part of AB quartet, J_(AB) =13.7 Hz),4.67 (1H, s), 4.82 (1H, s), 9.52 (1H, s); ¹³ C-NMR (75 MHz), δ 14.05,i7.36, 18.84, 24.94, 30.58, 34.07, 43.54, 46.89, 54.12, 115.69, 142.24,208.19; IR (Neat), 2960, 2700, 1730, 1645, 1470, 1370, 890 cm⁻¹ ; MS(m/e), 210 (M⁺), 195, 177, 154, 139, 126, 112, 97, 83 (Base);

Odor: Fruity weak

EXAMPLE 74 2-Methyl-2-(4,4-dimethylpent-2-yl)-4-pentenal (mixture ofdiastereomers)

In a similar manner to Example 6, 100 g of the aldehyde from Example 72at a purity of 96% (0.61 mole) in 50 ml of DMF, 80 g of potassiumt-butoxide (0.68 mole) in 500 ml of DMF, and 53 g of allyl chloride(0.69 mole) in 50 ml of DMF were reacted in the usual manner. In thisway 90.5 g of crude O- and C-alkylates (65.7:9.6) and 12.2% of startingmaterial were produced. The crude product was heated at 155°-170° C. for3 hours to afford 87 g of crude aldehyde. This material was distilled toafford 51 g of purified product (43% yield). BP 45° C./0.15 mmHg; ¹H-NMR (300 MHz), δ 0.89 (9H, s), 0.93 (3H, s), 0.94 (1H, m), 0.98 (3H,d, J=6.84 Hz), 1.2 (1H, m), 1.84 (1H, m), 2.18 (1H, m), 2.35 (1H, m),5.06 (2H, m), 5.67 (1H, m), 9.45 (1H, s); ¹³ C-NMR (75 MHz), δ 13.99,16.69, 18.15, 30.03, 32.54, 38.98, 46.38, 53.29, 118.23, 133.47, 207.26;IR (Neat), 2960, 2700, 1730, 1640, 1480, 1370, 920 cm⁻¹ ; MS (m/e), 181(M⁺ -15), 98, 83, 69, 57 (Base);

Odor: Fruity

EXAMPLE 75 2,4-Dimethyl-2-(4,4-dimethylpent-2-yl)-4-pentenol (mixture ofdiastereomers)

Similar to Example 7, 60 g of the aldehyde from Example 73 at a purityof 97.4% (0.278 mole), 125 ml of isopropanol, and 33 g of aluminumisopropoxide (0.153 mole) were refluxed for 1 hour. The usual work-upafforded 59.5 g of crude alcohol. The crude alcohol was distilled toafford 52.6 g of purified product (89% yield). BP 73° C./0.04 mmHg; ¹H-NMR (300 MHz), δ 0.86 (3H, s), 0.91 (9H, s), 0.93 (3H, d, J=6.6 Hz),1.4-1.72 (3H, m), 1.82 (3H, s), 1.90-2.15 (2H, m), 3.48 (2H, m), 4.73(1H, s), 4.85 (1H, s), hydroxyl proton exchanges out; ¹³ C-NMR (75 MHz),δ 17.24, 17.78, 19.17, 25.42, 30.22, 33.94, 41.66, 42.20, 45.48, 67.94,114.37, 144.67; IR (Neat), 3400, 2960, 1640, 1470, 1370, 1035, 890 cm⁻¹; MS (m/e), 197 (M⁺ -15), 181, 156, 137, 123, 109, 95, 83, 69, 57(Base);

Odor: Weak

EXAMPLE 76 2-Methyl-2-(4,4-dimethylpent-2-yl)-4-pentenol (mixture ofdiastereomers)

Similar to Example 7, 30 g of the aldehyde from Example 74 at a purityof 96.5% (0.147 mole), 125 ml of isopropanol, and 17 g of aluminumisopropoxide (0.083 mole) were refluxed for 1 hour. The usual work-upafforded 29.9 g of crude alcohol. The crude alcohol was distilled toafford 27.8 g of purified product (95% yield). BP 62° C./0.12 mmHg; ¹H-NMR (300 MHz), δ 0.73-0.93 (7H, m), 0.90 (9H, s), 1.37-1.65 (3H, m),2.09 (2H, m), 3.44 (2H, m), 5.06 (2H, m), 5.86 (1H, m); ¹³ C-NMR (75MHz), δ 17.13, 18.04, 30.23, 31.07, 32.72, 39.85, 40.97, 45.41, 67.84,116.94, 135.94; IR (Neat), 3360, 2980, 1640, 1470, 1370, 1040, 1025, 910cm⁻¹ ; MS (m/e), 183 (M⁺ -15), 157, 83, 69, 57 (Base);

Odor: Weak

EXAMPLE 77 2,2,4-Trimethyl-4-(4,4-dimethylpent-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 46.1 g of the alcohol from Example 75 at a purityof 98.3% (0.213 mole), 1.0 g of Amberlyst-15, and 150 ml of heptane wererefluxed for 1 hour. After the usual work-up 47 g of crudetetrahydrofuran was obtained. The crude product was distilled to afford44.3 g of purified product (98% yield). BP 43° C./0.15 mmHg; ¹ H-NMR(300 MHz), δ 0.90 (9H, s), 0.93 (3H, d, J=6.69 Hz), 0.9-1.25 (2H, m),1.02 (3H, s), 1.22 (3H, s), 1.30 (3H, s), 1.56 (3H, m), 3.54 (2H, m); ¹³C-NMR (75 MHz), δ 18.97, 20.55, 28.99, 29.77, 29.86, 30.23, 37.87,47.73, 48.97, 52.15, 77.68, 80.84; IR (Neat), 2980, 1480, 1370, 1060cm⁻¹ ; MS (m/e), 197 (M⁺ -15), 123, 83, 69, 57, 43 (Base);

Odor: Decatone musty

EXAMPLE 78 2,4-Dimethyl-4-(4,4-dimethylpent-2-yl)tetrahydrofuran(mixture of diastereomers)

Similar to Example 4, 22.5 g of the alcohol from Example 76 at a purityof 98.35 (0.11 mole), 0.6 g of Amberlyst-15, and 100 ml of heptane wererefluxed for 12 hours. After the usual work-up 23.2 g of crudetetrahydrofuran were obtained. The crude tetrahydrofuran was distilledto afford 19.6 g of purified product (89% yield). BP 34° C./0.04 mmHg; ¹H-NMR (300 MHz), spectra consistent with assigned structures; ¹³ C-NMR(75 MHz), spectra consistent with assigned structures; IR (Neat), 2980,1480, 1370, 1085, 1070; MS (m/e), 198 (M⁺), 183, 127, 109, 98, 83, 69,57, 43 (Base);

Odor: Fresh woody amber clean

EXAMPLE 79 2-[1-(4-Methyl-3-cyclohexenyl)ethyl]-4-methyl-4-pentenal(mixture of diastereomers)

In a similar manner to Example 6, 171 g of3-(4-methyl-3-cyclohexen-1-yl)butanal at a purity of 96.25 (0.99 mole)in 100 ml of DMF, 125 g of potassium t-butoxide (1.05 moles) in 600 mlof DMF, and 100 g of methallyl chloride (1.10 moles) in 100 ml of DMFwere reacted in the usual way. In this manner 212 g of crude 0- andC-alkylates were obtained. The crude product was heated at 165°-170° C.for 10 hours to afford 206.3 g of crude aldehyde. This material wasdistilled to afford 107 g of purified product (51% yield). BP 91°C./0.15 mmHg; ¹ H-NMR (300 MHz), spectra consistent with assignedstructures; ¹³ C-NMR (75 MHz), δ 12.93, 23.34, 25.65, 28.00, 30.56,30.69, 134.18, 143.24; IR (Neat), 2960, 2705, 1725, 1640, 1450, 1370,890 cm⁻¹ ; MS (m/e), 220 (M⁺), 205, 125 (Base), 107, 91, 69;

Odor: Fruity leafy green

EXAMPLE 80 2-[1-(4-Methyl-3-cyclohexenyl)ethyl]-4-methyl-4-pentenol(mixture of diastereomers)

Similar to Example 2, 90.2 g of the aldehyde from Example 79 at a purityof 94% (0.385 mole), 7.5 g of sodium borohydride (0.198 mole) in 250 mlof ethanol were reacted in the usual manner. After the usual work-up90.3 g of crude alcohol was obtained. This material was distilled toafford 26.7 g of cyclized tetrahydrofuran (see Example 81) and 45.8 g ofdesired alcohol (54% yield). BP 106° C./0.2 mmHg; ¹ H-NMR (300 MHz),spectra consistent with assigned structures; ¹³ C-NMR (75 MHz), δ 11.55,22.09, 23.39, 26.51, 27.92, 29.00, 30.90, 36.08, 37.32, 39.49, 64.97,111.70, 120.79, 134.00, 145.53; IR (Neat), 3330, 2960, 1650, 1450, 1380,1040, 890 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 189, 147, 133, 121 (Base),107, 93, 81, 67, 55, 41;

Odor: Weak

EXAMPLE 812,2-Dimethyl-4-[1-(4-methyl-3-cyclohexen-1-yl)ethyl]tetrahydrofuran(mixture of diastereomers)

Similar to Example 3, 70.0 g of the alcohol from Example 80 at a purityof 81% (0.255 mole), 0.35 g of p-TSA and 275 ml of hexane were refluxedfor 20 hours. After the usual work-up 70 g of crude tetrahydrofuran wereobtained. The crude material was distilled to afford 54 g of purifiedproduct (95% yield). BP 79° C./0.07 mmHg; ¹ H-NMR (300 MHz), δ 0.78 (3H,m), 1.20 (3H, s), 1.29 (3H, s), 1.2-2.1 (10H, m), 1.63 (3H, s), 2.40(1H, m), 3.44 (1H, m), 3.98 (1H, m), 5.38 (1H, br s); ¹³ -NMR (75 MHz),δ 13.98, 23.96, 25.98, 28.93, 29.40, 31.46, 31.53, 37.41, 41.48, 43.90,44.69, 72.30, 81.11, 121.34, 134.45; IR (Neat), 2980, 1455, 1365, 1055cm⁻¹ ; MS (m/e), 222 (M⁺), 204, 189, 147, 125, 121, 107, 95, 81, 67, 55(Base);

Odor: Green rosey weak

EXAMPLE 822,2-Dimethyl-4-[1-(4-methylcyclohex-1-yl)ethyl]tetrahydrofuran (mixtureof diastereomers)

Similar to Example 9, 35.7 g of the tetrahydrofuran from Example 81 at apurity of 97.2% (0.156 mole) were hydrogenated on a Parr shaker at25°-30° C. in 50 ml of ethanol using 0.75 g of 5% Pd on carbon. Afterthe usual work-up 36.6 g of crude product were obtained. The materialwas distilled to afford 34.4 g of purified tetrahydrofuran (98% yield).BP 75° C./0.10 mmHg; ¹ H-NMR (300 MHz), spectra consistent with assignedstructures; ¹³ C-NMR (75 MHz), spectra consistent with assignedstructures; IR (Neat), 2965, 1450, 1370, 1055 cm⁻¹ ; MS (m/e), 223 (M⁺-1), 209, 191, 151, 135, 123, 109, 95, 81, 69, 55 (Base)

Odor: Bell pepper green

EXAMPLE 832-(2-Methyl-2-propenyl)-3,7,7-trimethylbicyclo[4.1.0]heptane-2-carboxaldehyde(mixture of diastereomers)

A 4 neck 2 liter round bottomed flask was charged with 500 ml of DMF and78.0 g of potassium t-butoxide (0.66 mole). The flask was cooled to 0°C. and 100.0 g of 2-formylcarane at a purity of 75% (0.45 mole) in 75 mlof DMF were added dropwise over 30 minutes at 0°-5° C. The mixture wasstirred for 20 minutes at 0°-5° C. Then 60.0 g of methallyl chloride(0.66 mole) in 50 ml of DMF were added dropwise over about 25 minutesbetween 5°-12° C. The batch was poured with stirring into 2 liters ofcold brine and extracted with 3×250 ml of hexane. The hexane extractswere washed with 3×500 ml of water and 500 ml of brine. The hexane wasdried with sodium sulfate, filtered, and concentrated in vacuo. In thisway 127.8 g of crude product were obtained. The crude product wascharged into a 250 ml 3 neck flask and heated under nitrogen at165°-180° C. for 4.5 hours. The crude aldehyde was distilled to afford88.4 g of purified product (80% yield). BP 79° C./0.1 mmHg; ¹ H-NMR (300MHz), δ 0.6-1.0 (3H, m), 1.04 (3H, s), 1.06 (3H, s), 1.0-1.12 (2H, m),1.2-1.4 (3H, m), 1.6-1.8 (2H, m), 1.82 (3H, s), 2.44 (2H, m), 4.83 (2H,m), 9.63 (1H, s); ¹³ C-NMR (75 MHz), δ 16.44, 17.68, 20.06, 20.31,24.66, 27.04, 28.76, 31.24, 33.36, 40.74, 45.73, 49.66, 115.93, 141.89,204.41; IR (Neat), 2970, 2730, 1725, 1645, 1460, 1380, 895 cm⁻¹ ; MS(m/e), 220 (M⁺), 205, 191, 177, 165, 147, 135, 121, 107, 93, 81, 69, 55,41 (Base);

Odor: Camphoraceous

EXAMPLE 842-(2-Methyl-2-propenyl)-3,7,7-trimethylbicyclo[4.1.0]hept-2:yl methanol(mixture of diastereomers)

A 500 ml 4 neck flask was charged with 125 ml of dry isopropanol and 32g of aluminum isopropoxide (0.148 mole). The contents of the flask werebrought to reflux and then 60.0 g of the aldehyde from Example 83 at apurity of 93.8% (0.255 mole) were added dropwise over 45 minutes. Thereaction was refluxed for 1 hour. After cooling a Dean-Stark trap wasplaced on the flask and 128 ml of isopropanol/acetone were dwastilledout to a pot temperature of 107° C. After cooling to room temperature,the batch was extracted with 200 ml of 10% sulfuric acid and 200 ml ofhexane. The hexane was washed with 50 ml of water, 50 ml of 5% sodiumcarbonate, and 50 ml of brine. The hexane extract was dried withmagnesium sulfate, filtered, and concentrated in vacuo to yield 60.6 gof crude product which was distilled from 1 g of soda ash to yield 54.4g of purified alcohol (89% yield). BP 88° C./0.09 mmHg; ¹ H-NMR (300MHz), δ 0.58 (1H, m), 0.76 (3H, d, J=6.81 Hz), 0.97 (2H, m), 1.06 (3H,s), 1.14 (2H, m), 1.26 (3H, s), 1.50 (1H, m), 1.75-1.92 (2H, m), 1.84(3H, s), 2.1-2.6 (2H, m), 3.25-3.7 (2H, m), 4.81 (1H, s), 4.87 (1H, s);¹³ C-NMR (75 MHz), spectra consistent with assigned structures; IR(Neat), 3450, 2970, 1640, 1460, 1375, 1040, 890 cm⁻¹ ; MS (m/e), 222(M⁺), 207, 191, 167, 149, 135, 121, 107, 93, 81, 69, 55, 41 (Base);

Odor: Woody

EXAMPLE 85 6,8-Methano-3,3,7,7,11-pentamethyl-2-oxaspiro[4.5]decane(mixture of diastereomers)

A 3 neck 1 liter flask was charged with 218 g of the alcohol fromExample 84 at a purity of 89% (0.87 mole), 500 ml of hexane, and 2.5 gof p-TSA were refluxed for 24 hours. The batch was cooled and washedwith 250 ml of 10% sodium carbonate and then 250 ml of brine. The batchwas dried with magnesium sulfate, filtered, and concentrated in vacuo toafford 216 g of crude tetrahydrofuran. The tetrahydrofuran was distilledto afford 186 g of purified product (96% yield). BP 64°-69° C./0.25mmHg; ¹ H-NMR (300 MHz), spectra consistent with assigned structures; ¹³C-NMR (75 MHz), spectra consistent with assigned structures; IR (Neat),3005, 2980, 1460, 1370, 1065 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 192, 177,166, 149, 135, 121, 107, 93, 82, 69, 55, 43 (Base);

Odor: Timberol woody amber

EXAMPLE 863-(2-Methyl-2-propenyl)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl methanol(mixture of diastereomers)

In a manner similar to Example 42, 6.89 g of2,6,6-trimethyl-3-(2-methyl-2-propenyl)bicyclo[3.1.1]hept-3-ylcarboxaldehyde at a purity of 95.3% (0.03 mole), 0.56 g of lithiumaluminum hydride (0.014 mole), and 50 ml of ether were reacted in theusual way to obtain 6.7 g of crude alcohol (100% yield); ¹ H-NMR (300MHz), δ 0.99 (3H, s), 1.04 (3H, d, J=7.89 Hz), 1.21 (3H, s), 1.41 (1H,m), 1.89 (3H, s), 1.78-1.97 (4H, m), 2.1-2.6 (4H, m), 3.5-3.85 (2H, m),4.85 (1H, s), 4.93 (1H, s), OH proton exchanges out; ¹³ C-NMR (75 MHz),δ 17.09, 19.36, 23.50, 25.67, 28.39, 29.07, 35.77, 37.41, 39.24, 42.34,50.54, 54.03, 67.76, 115.78, 145.32; IR (Neat), 3400, 2950, 1640, 1460,1370, 1020, 890 cm⁻¹ ; MS (m/e), 207 (M⁺ -15), 191, 166, 149, 135, 121,107, 93 (Base), 83, 79, 69, 55, 41.

EXAMPLE 87 7,9-Methano-3,3,6,8,8-pentamethyl-2-oxaspiro[4.5]decane(mixture of diastereomers)

Similar to Example 4, 6.3 g of the crude alcohol from Example 86 at apurity of 95.6%, 0.75 g of Amberlyst-15, and 65 ml of hexane wererefluxed for 24 hours. After the usual work-up 5.8 g of crudetetrahydrofuran was obtained. The crude was distilled to afford 4.4 g ofpurified product (73% yield). BP 59° C./0.09 mmHg; ¹ H-NMR (300 MHz), δ0.89 (3H, s), 1.12 (3H, d, J=7.68 Hz), 1.19 (3H, s), 1.21 (1H, m), 1.26(3H, s), 1.29 (3H, s), 1.85-2.05 (6H, m), 2.15-2.25 (2H, m), 3.54(1H_(B), B part of AB quartet, J=8.8 Hz), 4.02 (1H_(A), A part of ABquartet, J=8.8 Hz); ¹³ C-NMR (75 MHz), δ 17.52, 23.16, 28.09, 29.55,29.95, 30.24, 38.41, 41.20, 41.47, 43.07, 46.22, 48.98, 65.31, 76.30,80.57; IR (Neat), 2970, 1455, 1370, 1070, 1045 cm⁻¹ ; MS (m/e), 222(M⁺), 207, 192, 180, 166, 149, 135, 121, 107, 93, 69, 55, 43 (Base);

Odor: Woody amber camphoraceous

EXAMPLE 881-(2-Methyl-2-propenyl)-3-(1,1-dimethylethyl)cyclohexane-1-carboxaldehyde(mixture of diastereomers)

Similar to Example 6, 17.0 g of 3-(1,1-dimethylethyl)cyclohexanecarboxaldehyde (prepared by the method of E. Heilweil and J. Virgilio,Organic Preparations and Procedures, 14 (1-2), 9 (1982) at a purity of87% (0.088 mole) in 20 ml of DMF, 11.9 g of potassium t-butoxide (0.10mole) in 60 ml of DMF, and 12.0 g of methallyl chloride (0.13 mole) in10 ml of DMF were reacted in the usual manner. The resulting mixture ofO- and C-alkylates, 21.6 g, was heated at 155° C. for 1 hour. The crudealdehyde so obtained, 19 g, was distilled to afford 8.7 g of purifiedproduct (45% yield). BP 57° C./0.1 mmHg; ¹ H-NMR (300 MHz), δ 0.85 (9H,s), 0.97-1.45 (3H, m), 1.66 (3H, s), 1.68-1.74 (3H, m), 2.03-2.40 (5H,m), 4.66 (1H, s), 4.84 (1H, s), 9.50 (1H, s); ¹³ C-NMR (75 MHz), δ23.26, 24.63, 26.60, 27.34, 31.40, 32.46, 33.79, 44.31, 47.74, 50.56,115.33, 140.77, 207.33; IR (Neat), 2970, 2690, 1720, 1635, 1450, 1360,895 cm⁻¹ ; MS (m/e), 222 (M⁺), 207, 166 (Base), 137, 123, 109, 95, 81,57, 41.

EXAMPLE 89 1-(2-Methyl-2-propenyl)-3-(1,1-dimethylethyl)cyclohexylmethanol (mixture of diastereomers)

Similar to Example 42, 8.19 g of the aldehyde from Example 88 at apurity of 90% (0.033 mole), 0.79 g of lithium aluminum hydride (0.019mole), and 30 ml of ether were reacted in the usual way to afford 7.63 gof crude alcohol (94% yield). ¹ H-NMR (300 MHz), δ 0.84 (9H, s),0.86-1.4 (5H, m), 1.55-1.8 (5H, m), 1.83 (3H, s), 2.01 (2H, m), 3.58(2H, s), 4.75 (1H, s), 4.88 (1H, s); ¹³ C-NMR (75 MHz), δ 22.34, 25.62,27.07, 27.46, 32.39, 33.11, 34.44, 39.26, 42.59, 49.46, 64.89, 114.29,144.37; IR (Neat), 3380, 2970, 1640, 1480, 1450, 1370, 1045, 890 cm⁻¹ ;MS (m/e), 224 (M⁺), 209, 193, 168, 151, 137, 111, 95, 81, 67, 57 (Base),41.

EXAMPLE 90 3,3-Dimethyl-7-(1,1-dimethylethyl) -2-oxaspiro[4.5]decane(mixture of diastereomers)

Similar to Example 4, 7.03 g of the alcohol from Example 89 at a purityof 92% (0.028 mole), 0.29 g of Amberlyst-15, and 60 ml of heptane wererefluxed for 24 hours. The usual work-up afforded 7.2 g of crudetetrahydrofuran. This material was distilled to afford 5.92 g ofpurified product (92% yield). BP 68° C./0.3 mmHg; ¹ H-NMR (300 MHz), δ0.88 (9H, s), 0.88-1.22 (5H, m), 1.25 (3H, s), 1.26 (3H, s), 1.57 (2H,s), 1.65-1.77 (4H, m), 3.62 (2H_(AB), AB quartet, J_(AB) =8.85 Hz); ¹³C-NMR (300 MHz), δ 24.31, 26.63, 27.51, 29.02, 29.27, 32.26, 36.92,39.38, 45.30, 45.53, 54.93, 74.33, 79.49; IR (Neat), 2960, 1450, 1360,1050 cm⁻¹ ; MS (m/e), 224 (M⁺), 223 (Base), 165, 123, 109, 95, 81, 67,57, 43;

Odor: Dry woody earthy

EXAMPLE 91

The compound of Example 85 was odor evaluated neat and found to possessa strong, predominantly dry, woody, ambery odor.

Separately, it was incorporated into a simple perfume composition at a7.5% level, with the following effect. The perfume composition withoutthe compound of Example 85 had a woody, musky, powdery odor. When thecompound of Example 85 was added, it gave strength and sophistication,imparting a dry, ambery odor throughout the composition.

    ______________________________________                                        Ingredient           A      B                                                 ______________________________________                                        BENZYL SALICYLATE    18.70  18.70                                             ISO EUGENOL HT        3.11   3.11                                             LACTONE MC-15/        1.91   1.91                                             PENTADACANOLIDE                                                               LYRAL                20.50  20.50                                             METHYL CEDRYL KETONE 27.74  27.74                                             PRIME/VERTOFIX CR                                                             MUSK KETONE          11.20  11.20                                             SANDELA/SANTALEX      9.34   9.34                                             COMPOUND OF EXAMPLE 85                                                                             0       7.50                                                                  92.50  100.00                                            ______________________________________                                    

EXAMPLE 92

The compound of Example 56, which exhibits a strong, wood amber odorwith a dry and powdery feel, was evaluated in the formulations shownbelow. When used at a level of 10% in a masculine fragrance, it createda warm woody middle note with a slight powdery feel. This chemical canalso be used in higher concentration along side citrus, herbaceous andoriental accords. It also blended well with a floral fruity compositionwhere it functioned as a support next to Methyl Ionones.

    ______________________________________                                        Item                   A        B                                             ______________________________________                                        Masculine Composition                                                         Armoise Oil Maroc Decolorized                                                                        10       10                                            Bergamot 131/2/1C      100      100                                           Bergamot Oil Zest Extra                                                                              100      100                                           Clove Bud Oil          12       12                                            Coumarin               10       10                                            Dimetol                 5        5                                            Dipropylene Glycol/DPG 263      263                                           Galbanum Coeur @ 10% DPG                                                                             30       30                                            Hedione                70       70                                            Hydrocarboresin SB      5        5                                            Iso Butyl Quinoline @ 10% DPG                                                                        20       20                                            Iso Propyl Quinoline @ 1% DPG                                                                        25       25                                            Labdanum Res Brut H @ 50% DPG                                                                        40       40                                            Lemon Oil California Distilled                                                                       100      100                                           Patchouly Oil Rustless Light                                                                         65       65                                            Petitgrain Oil SA Pure  2        2                                            Reseda Body @ 10% DPG   5        5                                            Styralyl Acetate       10       10                                            Tarragon Oil Extra/Estragon Oil                                                                      11       11                                            Thyme Absolute Spanish  5        5                                            Triplal @ 10% DPG      12       12                                            Compound of Example 56  0       100                                                                  900      1,000                                         Floral Composition                                                            Aldehyde C-10 @ 1% DPG 45       45                                            Aldehyde C-14          90       90                                            Allyl Amyl Glycolate @ 10% DPG                                                                       60       60                                            Allyl Cyclo Hexyl Propionate @ 1% DPG                                                                 9        9                                            Amyl Acetate 95/100% IS STD @ 1% DPG                                                                 60       60                                            Benzyl Acetate Extra   30       30                                            Calone 1951 @ 10% DPG  45       45                                            Citronellyl Acetate    30       30                                            Damascenone @ 10% DPG   3        3                                            Ethyl Butyrate FCC @ 10% DPG                                                                          9        9                                            Galaxolide 50 DEP      150      150                                           Helional               30       30                                            Hexenol, Cis-3- @ 1% DPG                                                                             15       15                                            Hexenyl Acetate, Cis-3-/LRG 1241                                                                     18       18                                            Hexyl Acetate @ 10% DPG                                                                              12       12                                            Laurine Pure           60       60                                            Lilial                 30       30                                            Methyl Anthranilate    24       24                                            Phenyl Ethyl Alcohol White Extra                                                                     60       60                                            Tagete Oil Standard @ 10% DPG                                                                        30       30                                            Triplal @ 10% DPG      90       90                                            Compound of Example 56  0       100                                                                  900      1,000                                         ______________________________________                                    

EXAMPLE 93

The compound of Example 85, which exhibits a very intense, strong,woody-amber odor, was evaluated in the formulations shown below. Whenused at a level up to 5% in a masculine fragrance, it enriched the bodynote and blended well with herbaceous and citrus accords. In a floralcomposition, it added a sparkling quality due to its intensity.

    ______________________________________                                        Item                   A        B                                             ______________________________________                                        Masculine Composition                                                         Armoise Oil Maroc Decolorized                                                                        10       10                                            Bergamot 131/2/1C      100      100                                           Bergamot Oil Zest Extra                                                                              100      100                                           Clove Bud Oil          12       12                                            Coumarin               10       10                                            Dimetol                 5        5                                            Dipropylene Glycol/DPG 263      263                                           Galbanum Coeur @ 10% DPG                                                                             30       30                                            Hedione                70       70                                            Hydrocarboresin SB      5        5                                            Iso Butyl Quinoline @ 10% DPG                                                                        20       20                                            Iso Propyl Quinoline @ 1% DPG                                                                        25       25                                            Labdanum Res Brut H @ 50% DPG                                                                        40       40                                            Lemon Oil California Distilled                                                                       100      100                                           Patchouly Oil Rustless Light                                                                         65       65                                            Petitgrain Oil SA Pure  2        2                                            Reseda Body @ 10% DPG   5        5                                            Styralyl Acetate       10       10                                            Tarragon Oil Extra/Estragon Oil                                                                      11       11                                            Thyme Absolute Spanish  5        5                                            Triplal @ 10% DPG      12       12                                            Compound of Example 85  0       100                                                                  900      1,000                                         Floral Composition                                                            Aldehyde C-10 @ 1% DPG 45       45                                            Aldehyde C-14          90       90                                            Allyl Amyl Glycolate @ 10% DPG                                                                       60       60                                            Allyl Cyclo Hexyl Propionate @ 1% DPG                                                                 9        9                                            Amyl Acetate 95/100% IS STD @ 1% DPG                                                                 60       60                                            Benzyl Acetate Extra   30       30                                            Calone 1951 @ 10% DPG  45       45                                            Citronellyl Acetate    30       30                                            Damascenone @ 10% DPG   3        3                                            Ethyl Butyrate FCC @ 10% DPG                                                                          9        9                                            Galaxolide 50 DEP      150      150                                           Helional               30       30                                            Hexenol, Cis-3- @ 1% DPG                                                                             15       15                                            Hexenyl Acetate, Cis-3-/LRG 1241                                                                     18       18                                            Hexyl Acetate @ 10% DPG                                                                              12       12                                            Laurine Pure           60       60                                            Lilial                 30       30                                            Methyl Anthranilate    24       24                                            Phenyl Ethyl Alcohol White Extra                                                                     60       60                                            Tagete Oil Standard @ 10% DPG                                                                        30       30                                            Triplal @ 10% DPG      90       90                                            Compound of Example 85  0       100                                                                  900      1,000                                         ______________________________________                                    

EXAMPLE 94

The compound of Example 8, which exhibits a strong woody amber odor witha green herbal note, was evaluated in the formulations shown below. Whenused at a level of 10% in a masculine fragrance, it gave a rich warmwoody character. This chemical can also be utilized up to 20% innon-floral creations. In floral compositions, lower concentrations ofapproximately 3-5% give a powerful middle note.

    ______________________________________                                        Item                   A        B                                             ______________________________________                                        Masculine Composition                                                         Armoise Oil Maroc Decolorized                                                                        10       10                                            Bergamot 131/2/1C      100      100                                           Bergamot Oil Zest Extra                                                                              100      100                                           Clove Bud Oil          12       12                                            Coumarin               10       10                                            Dimetol                 5        5                                            Dipropylene Glycol/DPG 263      263                                           Galbanum Coeur @ 10% DPG                                                                             30       30                                            Hedione                70       70                                            Hydrocarboresin SB      5        5                                            Iso Butyl Quinoline @ 10% DPG                                                                        20       20                                            Iso Propyl Quinoline @ 1% DPG                                                                        25       25                                            Labdanum Res Brut H @ 50% DPG                                                                        40       40                                            Lemon Oil California Distilled                                                                       100      100                                           Patchouly Oil Rustless Light                                                                         65       65                                            Petitgrain Oil SA Pure  2        2                                            Reseda Body @ 10% DPG   5        5                                            Styralyl Acetate       10       10                                            Tarragon Oil Extra/Estragon Oil                                                                      11       11                                            Thyme Absolute Spanish  5        5                                            Triplal @ 10% DPG      12       12                                            Compound of Example 8   0       100                                                                  900      1,000                                         Floral Composition                                                            Aldehyde C-10 @ 1% DPG 45       45                                            Aldehyde C-14          90       90                                            Allyl Glycolate @ 10% DPG                                                                            60       60                                            Allyl Cyclo Hexyl Propionate @ 1% DPG                                                                 9        9                                            Amyl Acetate 95/100% IS STD @ 1% DPG                                                                 60       60                                            Benzyl Acetate Extra   30       30                                            Calone 1951 @ 10% DPG  45       45                                            Citronellyl Acetate    30       30                                            Damascenone @ 10% DPG   3        3                                            Ethyl Butyrate FCC @ 10% DPG                                                                          9        9                                            Galaxolide 50 DEP      150      150                                           Helional               30       30                                            Hexenol, Cis-3- @ 1% DPG                                                                             15       15                                            Hexenyl Acetate, Cis-3-/LRG 1241                                                                     18       18                                            Hexyl Acetate @ 10% DPG                                                                              12       12                                            Laurine Pure           60       60                                            Lilial                 30       30                                            Methyl Anthranilate    24       24                                            Phenyl Ethyl Alcohol White Extra                                                                     60       60                                            Tagete Oil Standard @ 10% DPG                                                                        30       30                                            Triplal @ 10% DPG      90       90                                            Compound of Example 8   0       100                                                                  900      1,000                                         ______________________________________                                    

EXAMPLE 95

The compound of Example 56 was evaluated in a woody/sandalwood typeaccord for toilet soap. The addition of 10% of the compound to theformula enhanced the woody notes, supported the sweet, floral notes andadded an amber note, while rounding off the overall character of thefragrance.

    ______________________________________                                        Ingredient              A        B                                            ______________________________________                                        ALDEHYDE C-11 UNDECYLENIC                                                                             1.00     1.00                                         AMBROXAN @ 10.0% BB     3.00     3.00                                         AMYL SALICYLATE, ISO FCC                                                                              80.00    80.00                                        BENZYL SALICYLATE       100.00   100.00                                       CEDARWOOD OIL VIRGINIAN BROWN                                                                         40.00    40.00                                        CINNAMIC ALDEHYDE       7.00     7.00                                         CITRONELLOL AJ          50.00    50.00                                        COUMARIN                50.00    50.00                                        DIMETHYL OCTANOL        3.00     3.00                                         ETHYL VANILLIN          1.00     1.00                                         EUGENOL                 35.00    35.00                                        EVERNYL/LRG 1201        5.00     5.00                                         GALAXOLIDE 50 DEP       100.00   100.00                                       GERANIOL 600            40.00    40.00                                        GERANIUM OIL CHINESE    35.00    35.00                                        HELIOTROPINE            15.00    15.00                                        IONONE, ALPHA/IRISONE PURE                                                                            15.00    15.00                                        LAVANDIN GROSSO         35.00    35.00                                        MENTHONE RACEMIC        5.00     5.00                                         MUSK KETONE             15.00    15.00                                        MUSK XYLOL              30.00    30.00                                        PHENYL ETHYL ACETATE    7.00     7.00                                         PHENYL ETHYL ALCOHOL WHITE EXTRA                                                                      90.00    90.00                                        ROSE CRYSTALS/ROSONE    8.00     8.00                                         ROSE TW 62/4/IC         25.00    25.00                                        SANDALORE               15.00    15.00                                        VERTENEX                90.00    90.00                                        DIPROPYLENE GLYCOL      100.00   0.00                                         COMPOUND OF EXAMPLE 56  0        100.00                                                               1000.00  1000.00                                      ______________________________________                                    

EXAMPLE 96

The compound of Example 56 was evaluated in a floral/spicy/agresticformulation, which can be applied to a laundry detergent. The additionof 5% of the compound added depth and gave a woody/amber aspect to thefragrance, while it softened the sharp minty and camphoraceous notes.

    ______________________________________                                        Ingredient             A         B                                            ______________________________________                                        ALDEHYDE C-12 LAURIC @ 10.0% DPG                                                                     7.00      7.00                                         AMBROXAN @ 1.0% BB     2.00      2.00                                         AMYL SALICYLATE, ISO- (EXTRA)                                                                        100.00    100.00                                       ANISIC ALDEHYDE/AUBEPINE                                                                             15.00     15.00                                        AURANTIOL PURE         15.00     15.00                                        BENZYL SALICYLATE      100.00    100.00                                       BERGAMOT RN 76/2/1C    70.00     70.00                                        CINNAMON LEAF OIL BLEACHED/DIST                                                                      7.00      7.00                                         COUMARIN               5.00      5.00                                         CYCLAPROP              40.00     40.00                                        DIMETHYL BENZYL CARBINYL ACETATE                                                                     25.00     25.00                                        EUGENOL                15.00     15.00                                        FIXOLIDE               40.00     40.00                                        FLEURAMONE             1.00      1.00                                         GALAXOLIDE 50 DEP      60.00     60.00                                        GERANIOL 600           90.00     90.00                                        HELIOTROPINE           30.00     30.00                                        HEXYL CINNAMIC ALDEHYDE                                                                              70.00     70.00                                        INDOLE PURE @ 10.0% DPG                                                                              3.00      3.00                                         ISO EUGENOL HT         5.00      5.00                                         ISORALDEINE 70         70.00     70.00                                        PHENYL ETHYL ALCOHOL WHITE EXTRA                                                                     100.00    100.00                                       ROSEMARY OIL SPANISH   7.00      7.00                                         TERPINEOL, ALPHA/TERPINEOL 900                                                                       70.00     70.00                                        VIRIDINE               3.00      3.00                                         DIPROPYLENE GLYCOL     50.00     0.00                                         COMPOUND OF EXAMPLE 56 0         50.00                                                               1000.00   1000.00                                      ______________________________________                                    

I claim:
 1. A compound selected from the group consisting oftetrahydrofurans of structures 1 or 2, or tetrahydropyrans of structure3: ##STR120## wherein R is acyclic, where acyclic refers to a chain ofat least four carbon atoms substituted with at least three methyl groupsin the chain, mono carbocyclic, where carbocyclic refers to a ring of5-8 carbon atoms, and with at least two methyl groups on the ring, orbi-carbocyclic where bi-carbocyclic refers to two carbon rings, eachring having between 5-8 carbon atoms fused together, substituted with atleast two methyl groups, and where R₂ =CH₃, or higher alkyl group having2 to 6 carbon atoms, R₂ H, C₃, or higher alkyl group having 2 to 6carbon atoms, R₃ H, or CH₃, and R₄ and R₅ =H, CH₃, or higher alkyl grouphaving 2 to 6 carbon atoms.
 2. The compound of claim 1, which is6,8-methano-3,3,7,7,11-pentamethyl-2-oxaspiro[4,5]decane, including itsindividual diastereomers and mixtures thereof.
 3. An odorantcomposition, which includes a compound selected from the groupconsisting of tetrahydrofurans of structures 1 or 2, or tetrahydropyransof structure 3: ##STR121## wherein R is acyclic, where acyclic refers toa chain of at least four carbon atoms substituted with at least threemethyl groups in the chain, mono carbocyclic, where carbocyclic refersto a ring of 5-8 carbon atoms, and with at least two methyl groups onthe ring, or bi-carbocyclic where bi-carbocyclic refers to two carbonrings, each ring having between 5-8 carbon atoms fused together,substituted with at least two methyl groups, and where R₁ =CH₃, orhigher alkyl group having 2 to 6 carbon atoms, R₂ =H, CH₃, or higheralkyl group having 2 to 6 carbon atoms, R₃ =H, or CH₃, and R₄ and R₅ =H,CH₃, or higher alkyl group having 2 to 6 carbon atoms.
 4. The odorantcomposition of claim 3, wherein said at least one compound is6,8-methano-3,3,7,7,11-pentamethyl-2-oxaspiro[4,5]decane, including itsindividual diastereomers and mixtures thereof.
 5. The odorantcomposition of claim 3, wherein said at least one compound is2,4-dimethyl-4-(3,3-dimethylbicyclo[2.2.1]heptan-2-yl)tetrahydrofuran,including its individual diastereomers and mixtures thereof.
 6. Acompound according to claim 1 of structures 1 or 2, wherein R₁ =CH₃, orhigher alkyl group having 2 to 3 carbon atoms, R₂ H, CH₃, or higheralkyl group having 2 to 3 carbon atoms and R₄ and R₅ =H, CH₃, or higheralkyl group having 2 to 3 carbon atoms.
 7. An odorant composition ofclaim 3, wherein R₁ =CH₃, or higher alkyl group having 2 to 3 carbonatoms, R₂ =H, CH₃, or higher alkyl group having 2 to 3 carbon atoms andR₄ and R₅ =H, CH₃, or higher alkyl group having 2 to 3 carbon atoms.